JPS59104642A - Method and material for reinforcing contrast of image - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention describes a method for enhancing the image of an object such as a mask for a true etching engraver in a permanent structure of an integrated circuit. This is related to kidnapping fees.

Photo-etching processes for the manufacture of integrated circuits are primarily carried out by optical means.In the drive to reduce circuit dimensions, improve performance, and increase yields, The resolution required in connection with each generation of two-circuit technology has been achieved by optical devices. It is now nearing the physical limit. As photoetching technology continues to progress, the unique lens solution of 1'4 degrees is 11 degrees. We cannot hope to improve the target 41.In order to further reduce the smallest details achieved by optical technique 1. It is necessary to aim for further improvement.One of the 41 areas where further improvement is possible is ``C 1 ~ Regime 1 ~ Operation 1. There is a characteristic that there is a necessary C゛ for one time in order to get rid of Bakun, who uses 1 history and 1 Ko 1.

Ko (7) J, tsu % minimum J! Ii illumination required]n1-ras1~ is called the threshold value for small1-resis1. Depending on the properties of the heavy plate, the required backing thickness, and the shape of the end of the photoresist 1~, the conventionally used positive type 11\1~Regime 1~ has 85~90% of the thickness of the photoresist 1~
At present, most production is performed under a contrast of 1- or more than 90%.By the way, the contrast of 1- or more of an image is due to an increase in the spatial frequency in the image. Therefore, if the contrast l-threshold value of the older brother C1 heregis 1- is lowered, the resolution that can be achieved using a certain optical device will be improved.

The present invention is directed to an operation in which the aerial image used in the operation is enhanced in advance of the large river to the resist. There is C of b regarding.

One of the objects of the present invention is to avoid lowering the minimum contrast 1 which is necessary to produce a usable 4ζ image in a small 1 heregis 1.

Ma/, :, Novel light 11) Compound J”i J capable of one color
It is also one of the objects of the present invention to provide a substance that has the following properties.

According to a certain implementation example 5 and below, to describe the CA invention, the first
1? A resist layer with a predetermined -J non-1 hellas I-small 1-resist layer is prepared. In addition, a subject or a mask is prepared that covers the opaque area J3 and the transparent area. By projecting the light of a constant wave beam through such a subject,
1) I skin 'L1'(4-'s ( A; is formed on one layer of the resists 1 and 1. Between the subject and the resists 1 and 1, light 11tJ (u iJ
A functional material layer is adjacent to the surface of the photoresist layer and has a C configuration 11.
’ will be done. Such light IBJ (U compounds are sensitive to light of the above wavelengths and are non-1 [(J3) in the one-color state.
The extinction coefficient/molecule Ii ratio of Rirudere is greater than p/ke·CTII units rIL. Also, the ratio of the extinction coefficient in the non-bleached state to the extinction coefficient in the 1j; two-color state is also 10.
More friendly. Through the subject (C above wavelength a3 and specified intensity)
Light 11; two-color IjJ-capable object lI'Ii Throw the light for a certain period of time on the layer q, j, 41 possible things'i1
A decrease in the degree of ℃ 1 of the layer will occur. As a result, the integral of the image transmitted through the layer of light 1
(1-las1) thereby increases with the amount of light passed, reaches a maximum value, and then decreases. light) 111
The parameters of the color-controlling material layer are
The maximum value of is set to be larger than the threshold value of the constant -j trass 1 of the bottom 1 heregis 1. Also,
The sensitivity of the photoresist layer is determined by the amount of light transmitted by the one-color material layer within a predetermined range and completely sensitizes the photoresist layer, and the amount of light transmitted by the one-color material layer completely sensitizes the photoresist layer. The predetermined integrals are set so that a predetermined integral is obtained. A port 1 for projecting light of the above-mentioned wavelength through the object is a light 11;
Take %f or enough to be transmitted. Hikari IB2 (
! After removing the 2iiJ-capable material layer, the volume 1-
Developing the eyebrows produces an enhanced pattern of 21[-cis1-] in the photoresist layer compared to the lower image of the subject.

The present invention also provides absorption within the range of 300-450 nm (
4! 1. A spin-castable mixture that forms a photobleachable layer. Such a mixture has (A) 100
The stone in the Φω part is a solvent, (B) 1 to 30 weight ω part, preferably 5
~15 parts of inert 411 coalescing binder, J5 and (C
) 1 to 30 parts by weight, preferably 5 to 15 parts by weight, of arylnitrone.

The novel features believed to be unique to the present invention that i<+-,G are described in detail in the scope of the previous i1j 'BJ i+'l crystallization, and apart from -C1°, the present invention's 414 The method of construction and implementation, as well as other features and advantages, may be best understood by reading the following description in conjunction with the accompanying drawings.

At present, most of the photo-etching operations use the aerial image of the mask. In the case of the aerial elephant of ~, the part of the image that corresponds to the dark area of the sky is also quite strong. Identification is becoming more and more IN!
According to the present invention, 4f plus 1 to i''+1 is provided. Ru.

This contrast enhancement is based on the use of a color-capable material that is initially relatively opaque but becomes relatively transparent after exposure to a small amount of light. The light transmittance of the two-color layer is shown in Figure 1 as a small J
. When the aerial image of the mask is incident on such a layer, 11(2
Color-+jl ril; The back of the layer C゛The part exposed to the highest intensity is the first J"complete 1[;(colored-/j, the part exposed to the lowest intensity is closer The color is bleached.

Such 1; (111 transition of color overgrowth is shown in Figures 2A-2F. Figure 2A shows an opaque area J'3 giving 0% transmission 11 and an open area J'3 giving 100% transmission 12. Or, the relative transmittance of an object such as a mask consisting of a transparent area is reduced. 1o is the intensity of the required light, ■ is the intensity of the transmitted light,
and b is the amount of light required to cause bleaching of the layer. FIG. 2B shows the appearance of an aerial image 111 when the mask is placed in an optical projection device for producing an aerial image useful for sensitizing, for example, a photoresist layer.
Graph 13 shows plots of intensity as a function of position.

J3, the likely wavelength used to cover J5 and N of each area of the mask
It is tentatively suffice to say that the law is just as illustrated.'' I m aχ is the maximum strong wind of the statue, and 1. . i 11 is the minimum intensity of the image. Figure 2c shows the idealized light 1152-colorable object vi layer 15 W' plane. Figure 2D shows the 14th/) 115 point J3
The decolorized state of the liquid layer 15) is represented by the dotted line 16. Figure 2L shows that J > 4 at a later point in time.
- The IIi color state of the layer 1) is expressed as J in the hot wire 17. Figure 21 shows C1 after exposure is completed.
1i'a color stopped 11,1 J3 riruk<i 15
l] f2 ('x state is represented by dotted line 1ε3 a3 yohi 19, ', C. Second, l corresponding to the figure
+, 'The lifting platform where the exposure was stopped at J3 at point J, lLi1
Transmittance of 5 (equivalent to the transmittance of a mask of 9).

This j, U4 "Thing 1'IC゛Usual small registers 1-I (
? The compound that can be coated with 1!7 is 1~resist layer only.
The low con I~las l~lJ'Alf+ is righted and 1'A is turned. This is possible only with Ho1~Resis1-0]
The sensitivity is high for 11 minutes (!21+: Compared to J, the sensitivity is high for 11 minutes.
i2 e il Noh 41 things! The first layer is water 1:r; from a perspective, it is a small tres l-h·'1-1. The true effect of this mask is that the real effect of this mask is that the mask is formed directly on the mask. The objective is to increase the distance from -1 to last of the aerial image.

(3.) When applying the contrast 1~enhancement technique to the Nabumicron photo-etching operation, U +, 1,''n 1~
Lass 1 - There are several physical and chemical constraints regarding the enhancement layer itself.1. ! Jru. -Tsunawara,'n1~
If the last enhancement layer is thin, the optical aperture must be high (J). , I
I,' is limited to a range of about 1 micron or less, 1,=
1] - the last enhancement layer has a high optical Ω anti-reflection <', N It
:) Since this must not occur, the photochemical component of K.1 must have strong light absorption (!-Y-J-). Therefore, the photochemical product has an extinction coefficient that is much smaller than that of the parent molecule J:OJ.

By the way, the extinction coefficient is defined by the following formula: 1° where 8 is the absorbance or the optical path length (cm), and C is the concentration (mof/f). (defined by)

In the formula, 1() is the intensity of the required light, and -U I 1. The intensity of L transmitted light is high. The extinction coefficient ε of a substance can be determined by adding C to the parameters in equation (1) by
C is required. Parameter A is obtained from equation (2). First, the concentration C of the substance in the Ci8 liquid is determined by dissolving a known weight of the substance in a known volume of solvent. This Raku1k'M is injected into a known private cell and the spectrophotometer is 1.
1, and the light with a known intensity of 10 is placed in the optical path of Hill I.
Say 〇・1 to J. Next, the intensity of the transmitted light from the cell is measured. Similarly, only the solvent is injected into another cell of the same known dimensions and then placed in the optical path with a spectrophotometric intensity of 1.1 and a known intensity I. of light entering the cell. Next, the intensity of the transmitted light from the leech is measured. The solvent-only intensity measurements are used to correct the -C transmission intensity I for absorption by leeches and solvent. By substituting the values of the incident intensity 1oJ5 and the transmitted intensity 1 thus obtained into equation (2), the absorbance can be obtained. The optical path length is determined from the known dimensions of the cell. This is how 114 b was done,
CJ3. , l; By substituting Mi of A into equation (1), the extinction coefficient of this substance can be determined. In addition,
The method for determining the extinction coefficient of a substance is as follows: 1-1old
, Iken1nel+art & WinsLon,
Published by I'nc, )
0(ItJ!as l\, 3'koog &
l) 01ldfvl, West) 't
ζ [Funtlamcntals of, A,
++alytic Cl+cmistry), 1st 2nd
rJi (1969), 644-6;] 2 It is also described in Tei.

Again, the quantum yield of the bleaching reaction must be as high as possible in order to minimize the increase in exposure time. Since it is a concave hole that is installed in the technology, it is convenient if the = 1 - 1 ~ rest reinforcement layer is installed in the same way -C.In addition, light 1j: 2 colors are possible. /i
Bathing in substances? The designated solvent must be compatible with the photoresist layer. C
Light q'1'-+'j! Is it possible to form a good ``n1~last monk h''j of i?/i:().

Finally, the wavelength range in which these photobleachable materials operate is not the same as the wavelength range in which optical projection equipment operates.
to++maf=LJ 436 nm (D wavelength
Written by l'JJ ``J'?,＞.

This is located at Mount 1, Mount 1, California, California, United States.
++Limctrix Co, ) to manpower! l
A Zodimetrics 10:11) SW installation 100 J3 C
The wavelength for use was 40:) nm or 8). While considering these constraints, the search for the substance that controls light 11iJ (!v) was carried out.1.
At the point where the absorption maximum is within the wavelength range of 0111n,
rj IJ L 'C light) 1; A substance capable of two colors was searched.

In addition, a model of the decolorization process was devised for use in evaluating materials capable of two colors of light suitable for use in C in the enhancement layer. The parameters of such a model are summarized in Table 1 below.

Table 1 Explanation εA Extinction coefficient εt+ of non-bleaching molecule Absorption coefficient of IBJ molecule
1j; Quantum yield No. of 1-eup reaction First of non-1112 color molecules! 111 Honey Melon 1o Contrast l-Unsweet Melon of the photon incident on the enhancement layer [0 Con 1 - Last Enhancement h・) of 71. “Sa+1.
Based on the above analytical results and the model of the color process, three criteria regarding the parameters of the material are: They are shown in Table 2 below.

Second table tli
I+self(1)ε/molecule t^
＞100 J / 9・mark (2) φ ＞
0.2 (3) Non-1 [; 2-color n5 >30ε/IB1
The first group 11 (is based on the requirement of a film with a high optical temperature), and in terms of wood quality, J3 is included in the contrast enhancement layer.
-C is related to the packing density of the absorption center of Cl. The second standard is based on the four rapid transitions from the chain state to the 1152-color state. To some extent, whether or not is the first
7. %il! ', Seki 1 Ito Rir 1, Na 1! ″, then
There is C because it is possible to compensate for the lack of C second prefecture by changing the first one. The third criterion is based on the requirement of transparency of the 1-Las 1-enhancement layer after decolorization.

The use of these criteria first led to a search for photobleachable substances.

Appropriately 4, light 1j; C in selecting a monochromatic compound is 11
(In addition to conducting evaluations on the model of hyperchromatic culm, we also conducted tests on layered compounds to determine the relative transmittance as a function of time or light intensity when the intensity of light was kept constant.) Shows 1112 color properties based on different decolorization mechanisms.
After evaluating various photo-111 dichroic compounds, it was found that photo+j+X photo-chromic compounds by photoisomerization are particularly suitable. Among these compounds, arylnitrones of the formula % have been found to be particularly suitable. In formula (1), / is the formula (+<3)a-Q-R'
- or a monovalent group represented by [5-, /-μ formula -R
'(X) bCi<wa cs cell I l1lb(
7) J4, - and τIR1R', F<2j'jyohiR
3 is a hydrogen atom, C(1-8>alkyl group, C(1・-8
) A monovalent group selected from BY consisting of a substituted alkyl group, C(6-13) aryl hydrocarbon group, and C(6-13) 1':i ground aryl hydrocarbon group. Q is 1
:, C-, L+rr, o, sa>, and fiY consisting of N
J is a selected monovalent, divalent or trivalent atom,
And a takes a value of 0.1 or 2. R4 is C(
6-13) i' aryl hydrocarbon group or C(6 to 13) 1iff-substituted aryl hydrocarbon group C. R
5 is 0. NJ>J: 1 selected from S 1 [! ,
Substituted or unsubstituted C containing 1 or more 1 quintillion f (6 to 20
) JiY consisting of an aromatic heterocyclic compound. R6 is a C(6-20) aromatic hydrocarbon group, and X is a halogen atom, a cyano group, an alkyl group, a C(1-8) alkyl group, a C(1-8) substituted alkyl group, C (to G・i 3 > aryl hydrocarbon), t
, 0(6-13) iffil' force i1 reel hydrocarbon group OJ, pial'4'l consisting of xical hole group j
These J, t are the sum of fi1 of 0, 0, 2 or 3, respectively.
Use it or use it. n takes a value of 0.1.2.3 or 4.

The compound of 1- is lj.Ubenuuair (1-l
oubc++-Weyl > SL+i
den dcr Organisclalan Che
n+ic)” Volume 10, Part 4 (19 (1958), Part 3
15-416 True J, or [Chemical Levicause (C
chemical review) J 1st (6/1
J anllamcr & antbony in vol.
Ivlacaluso) Xi to l-rons (N 1
The C adjustment can be carried out according to the method described in J. Trones J, pages 476-483.

A variety of aryl ring systems can be constructed with various modifications to meet the specific requirements of the optical equipment used in J3 photolithography operations.

Such arylni1~rons are 2~bX104j! /m
The extinction coefficient of ol-co+ is 1], and 0.1 to 0.5
T-11i has two colors with a quantum yield within the range of .

If projection is possible at 405 nm (for direct processing), the general formula (where 1) is Oj, /, - has the value 1) The 21 to 1 condyle shown in Table 1 has been found to be particularly useful.

Among this type of p-dialkylaminoaryls, there are also included heterocyclic compounds represented by the formula 'C'.

The light that illuminates the aryl group of formula (1) (1j)
Vinyl acetate polymers (li monopolymers and copolymers) as suitable binders to aid in the preparation of rotary castable mixtures for forming single-color materials. or partially saponified products thereof (for example, polyvinyl acetate), copolymers of sutyrene or its derivatives, monopolymers and copolymers of acrylic acid J or methacrylic acid ester, aretal resins, acryloni-1-lyl butadiene copolymers, ethyl cellulose and other hydrocarbon-soluble hirulose nitrates, propionic acid 1'-ose and other hydrocarbon-soluble cellulose esters, boric[10-brene, voriconythylene A oxide and polyvinyl vinylidene]. can be mentioned.

The aryl nidrones of formula (I) are
Suitable solvents to aid in the preparation of the moldable mixture on the rotary T to form the colorable material layer are aromatic hydrocarbons (e.g. toluene, xylene, ethylbenzene, chlorinated benzene, etc.) or aromatic hydrocarbons and fatty acids. Examples include mixtures of group hydrocarbons (for example, hexane, etc.), aliphatic hX compounds (for example, 1-lichloro-1-burene, methylchloroform, etc.), and alcohols (for example, propatool, butanol, etc.).

Particularly preferred are diarylnitrones of formula (It) in which (1<3 is Cf-13GHz- and 1) is O. This compound, called nyl)-N-phenylnide[an, can emit light with a wavelength of 405 nm?J
E,', <absorbs but nE] to the same wavelength with high efficiency in A5-C1112 color. Such a color occurs as a result of this compound undergoing monomolecular cyclization to form -C. This compound is relatively small and extremely soluble in solvents (e.g. toluene, -thilbene, etc.), and methacrylate), poly-alpha-methylstyrene, poly(methylmethacrylate-1~), vinylylvinylidene lydone, hinylpyricine styrene ξ polymer, J: allyl alcohol,
-1・'C' of styrene polymerization 1. ,! A good<k film is formed. alpha
-Jl-fu' = Nilu I-Ul'/4ma40ri ++m smell-(130j!/'it・CTI
I's 1y & light faction/molecule ζ1 (ratio is A). In order to form a helast-enhancing layer containing the compounds in the mouth, first, a proportion of b (car weight)% (α-(4-diethyl/minof1-nyl)-N-phenyl-2-1-1 and 5-(I)) was added. amount)%
Dissolve the styrene-allyl alcohol co-alcohol binder in 1 l:. Then, using the diluted solution, the thickness of 25 Q TlIn is obtained. When a 405 ntnC test was conducted on a 31-phase key with a 1° rotational angle, it was found that the relative transmittance time characteristic as shown in Figure 3 was obtained. .

By using the model of the bleaching process, the contrast 1 to enhancement N? in Figure 3 can be improved. The degree of improvement of 11-1 to 1-1 related to i was determined as a function of exposure history. Part 1
In this case, VJ1 is applied to two representative points in the predetermined pattern.
All you have to do is calculate the degree of lffi color. This example C' is a grid pattern consisting of lines a3 J: and gaps with a maximum of 11fI.
Two incident intensities were chosen that corresponded to the minimum value of a3 J. =1-1~Last l-C corresponding to these two intensity levels can be derived from the following definition equation of J, Una 2-1~Last.

1[j (by using the color process model, the maximum level d3
and the minimum level (the transmitted intensity at J5 is a function of the light intensity of the person QJ and is determined by -. From these 10, y1:221 ntrus 1 to J3 and the integral contrast 1- are a function of the light intensity of the person01, and ;1st style J8S can be made.Figure 4 is as follows.
Show the measurement results and measurement results when you avoid using the pattern of 30%-1 nt truss I for the above-mentioned trial! Graph 21 shows the relative transmittance at the relative maximum level as a function of the amount of incident light in Joules. Graph 22 is
Phase 34 The relative transmittance of J>Ij to a small level of Jia is shown as a function of light. Graph 23 is obtained from C graphs 21J3 and 22 using equation (3).
c@It;) 2'n1-last is shown as a function of the amount of incident light. Graph 24 shows I m a x J> and Im+. Integral 1111 instead of threshold 11-71+1i
From equation 0 (33), use j sumera! The contrast is 1 for ζTri.

1112 colors are IuJ-like overcultivates (゛), so they are a function of the amount of light due to the amount of transmitted light. As a function -C
A typical graph of Ishikawa is shown. Using these graphs, it is possible to use the culm 1 layer of the layer 1 to enhance the contrast with the contrast enhancement layer as a function of the effect of the small tres layer 1 to the contrast enhancement layer. Graph 26 shows the relative transmittance at the relative maximum as a function of the amount of transmitted light.

Graph 27 shows the relative transmittance at the relative minimum level J3 as a function of the amount of transmitted light.
The instantaneous II\contrast l- obtained from the graphs 26J3 and 27 using equation (3) is expressed as a function of the amount of transmitted light. Graph 29) shows l m a x J3 and 1
The integral values 1 to 1-, which are obtained from equation (3) using the integral value of fflin, are expressed as a function of the transmitted light 1i.

Next, we will describe a method for utilizing such contrast enhancement layers and then compare the results obtained by that method to those obtained under the same conditions without the use of contrast enhancement layers. Compare the results. The following explanation is for the appropriate IB
(Refer to Figures 1'J and 6A to 6, which illustrate the various techniques for forming the patterns of 1st grade to 1st grade on the autumn top.)

Figure 6A shows the installation of an appropriate elementary school 1~regimen (j32) on the base] k31 ten.
~Regime 1~ and C are, for example, Sibley Company (SI), located in Nicolne Mountain, United States of America.
For example, there is a positive type photoresist of the Shivsea 1400 series that can be made by hand. Gagaru positive type car 1 ~ Regis 1 ~
The composition consists of a novolac tEJ resin or poly(vinylphenol), a diazonano-1 hegenone, a diazonol ester, and a small solvent (e.g., Urosolver, U-1, or xylene). The liquid resist is placed on the surface and then rotated to form a desired thickness of h'4. After removing the solvent, an enhancement layer 33 is placed on the surface of the resist layer.
The enhancement layer 33 contains 5 (i[#T,
)% styrene-allylic alcohol polymer binder (
Bath 11 in which 13 J and 5% (by weight) of α-(11-diethylaminoJ-nyl)-N-phenylnide were dissolved.
There are C consisting of K. Poresis 1 layer 32 of this solution
613, a layer 33 of the desired thickness is formed, as shown in FIG. 613. The structure thus obtained, as shown in Figure 6C, shows the J arrow 3
7 lower) illumination=I area IfA35 J>Yohi is wiped away by a light pattern consisting of the non-irradiated area 36. Such an operation is carried out until the resist layer is sensitive and the photoresist layer is completely sensitized;
, -1-1~C for a sufficient period of time to produce an enhanced image of last? -J gets caught. Thereafter, as shown in FIG. 6D, the enhancement layer is removed without affecting the photoresist layer without affecting the photoresist layer.
, 1j using a solvent remover (e.g., Tric LI II) is used to remove C:Jn 1~Las 1~enhancement layer 33. Next, remove the photosensitive parts of the layers from Hole 1 to Resis 1, and the 6th layer is removed.
As shown in Figure E, non-exposed or incompletely exposed areas 38.39 J-3 and 40 remain.

1. Two trusses obtained according to the invention for a composite of a contrast-enhancing layer and a resist layer.
Toward the actual ii + [-! In order to obtain the above light 1j; one color capable substance consisting of α-(4-di'tylno'minophenyl)-N-phenyl-throne and styrene/)7lyl-alul co-j13 combination, the Shipley 1400 series Various patterns were formed using positive type photoresists. , that is, the first silicon layer is coated with only a 1.6 μm thick photoresist.
, a second silicon wafer is coated with a photoresist layer J> of 1.6 μm thick [1 μm] and a layer of photoresist J> of 0.25 μm thick [1−1 μm].
1; (covered with a layer of colorable material 47 L, then C', 2 µm wide) opaque line, 2 µm wide transparent gap, 0.8 µl wide opaque IpJ An object consisting of a line and a transparent gap with a width of 0.8 µm was illuminated with light at a wavelength of 405 nm using a 1 to 10:1 projection device. By using a range of light intensity, small 1
~Only resist 1 is applied to the wafer, and a visible pattern is projected in the layer to regime 1, and the pattern of vision is projected in the layer to regime 1. Multiple patterns were also projected into the photoresist layer of the wafer. When each of the photoresists 1 to 1 to 3 stones were developed, a line a3 was formed in the photoresist layer.
A pattern of 9, consisting of J, and gaps, was created.

By using the minimum light intensity that creates a gap of t15 - U08 micron at the interface between the photoresist layer and the base, only the small tresist layers 1 to 1 are irradiated.The pattern obtained by applying J3 to the wafer is The photoresist layer A5 and the contrast layer 1 to the enhancement layer 1 to J3 were obtained by using a minimum light intensity that produced a gap of 0.8 microns between the d3 and the substrate and compared with the IC pattern. . For both wafers with only a photoresist layer and wafers with resist layers and contrast-enhancing decoys, widths of 2.0 µm [1 in. The gap was approximately appropriate. Ho 1 ~ Regime 1 ~ Only touching the mouth "A3 °C in the shaver,
When using a light intensity that produces a gap of 0.8 microns in width in E1~Register 1-V1, a line with a width of 0.8 microns is approximately -
(Excessive exposure. However, small 1 to resist I'i
For a wafer with an enhancement layer placed on the resist layer 1 and 1, the width of L1 is 0.8 microns when using a light intensity that creates a gap of 0.8 microns in the resist layer. The line is moderately exposed and has a width of 0.0 mm during the photoresist process.
A line of 8 microns [-1 nm] was produced. Historically, the sidewall of the pattern that received reinforcement from Con 1 ~ Las 1 ~ was almost at the center of gravity C.

The poor quality of the J5, 21 and 1-regimen 1-1 (1 in 1!) without last enhancement layer is due to the poor quality of the pattern obtained from the This is because the spatial frequency in the aerial image obtained is j'l''I<, and therefore the contrast of the aerial image is low.

Although the present invention has been described above in relation to positive type vehicle registers 1 to 1, which are constant, other positive type vehicle registers 1
- J3, negative type, E1, Resis 1, can be used.

In addition, in J5, a small resist layer J3J of a specific thickness J, (of a constant thickness J''F)
It is possible to use the small resist layer and the other J'; It is recommended that the eyebrows have a thickness of about 3 microns or less, and the helasto-enhancing reservoir should preferably have a thickness of about 1 micron or less! .

In the composition of the above-mentioned layer 1, light 11; (chromic compound JjJ, binder) were used in equal weight ratios, but other ratios may be used if desired. is also possible.

In the above, it was stated that Elementary 1~Regime 1- has a property called the last threshold for 21/1, but this property applies not only to Small Tregis 1 itself, but also to the usage conditions of Elementary 1~Regime]-. For example, it is important to pay attention to the nature of the substrate used and its reflectivity.

Regarding photobleaching compounds, C is non-1j1 (extinction coefficient/molecular weight ratio in the color state is about 100 J, larger and non-!j;
It is said that it is preferable that the ratio between the extinction coefficient in the color state and the extinction coefficient in the one color state (11) is greater than about 30. However, the value of these ratios is about 10C You should get the results you want.

In the above, the d3 C is not seen in the middle molecule cyclization. i version J3
It is highly unlikely that other photobleaching compounds that adhere to the 11) two-color mechanism (eg, photocleavage) could also be used in accordance with the present invention.

The above-mentioned stiffness is summarized in the following Table 3. mole) of p-G1
．． delaminobenzaldehyde and 11, /+9(0
, 1 mol) of fresh phenyl with 1-U xylamine in 110 m anhydrous ethanol at room temperature.
It was conducted for 8 hours. Evaporate the solvent and recrystallize the red oily substance twice from chill. +
:, i is not 13.0'; , i is 110-112
By °C ('') Two worlds 1.:.

In Table 3, there are 43L], 300-45) 011010 waves, absorption within the range of 1 (4!) and other 21-
The uncondyles are also small (in Table 3, λ, .aX(1
11n) represents the position of the absorption maximum of the nonomer lJi (j), ε"118χ represents the extinction coefficient at the wavelength of absorption of (111), and n represents the Celsius drama!li
(Represents the melting point of m.

As in the case of 21.1'' above, a suitable aldehyde and phenylhydro-1-
1゜This J2I] was prepared by condensing d5C with Zylamine in a 44A solvent. The material layer forms a mask formed directly on the photoregimen hIP,i. Forming such composite structures has several advantages. Since the photochromic material layer conforms to the surface shape of the photoresist layer, the formation of voids between the high points on the surface of the photoremovable material layer and the photoresist layer is avoided. It will be done. Such a gap would occur if the two layers were formed on separate supports 111\ and avoided contact from 'C'; such a gap would be critical to the resolution of the image formed in the small herecyst layer. C) Heme (a) Harm - C, especially the formation 8Jl\sa'' details\
If the J method is the micron culm, then the focal length of the projection device is 1 or the micron culm is 1, L if it is. ζ、Hikari 11shi (If Imochi fil na goods trade red 1 is pulled away after avoiding contact with Kotoresis I, -)
There is a risk that fragments of the 'no layer will fall onto the other force layer and the small tresis layer 1 to 1 will be damaged.

In the detailed description of the invention, it has been described that the enhancement layer is placed in contact with the resist layers 1 to 1 for the contrast 1, but if desired, for example, a thin intervening layer of a neutral material may be formed. The contrast enhancement layer can be isolated from the photoresis layer 1 by photoresis.

Although the invention has been described above in connection with specific embodiments, it will be obvious to those skilled in the art that modifications and changes, such as those described above, may be made. Therefore, so long as the scope of the claims does not depart from the spirit and scope of the invention,
It should be understood that this is intended to cover all such modified embodiments.

[Brief explanation of drawings]

Figure 1 is a graph showing the relative transmittance of an idealized decolorizable layer as a function of the amount of light incident on its plane of incidence; To illustrate the course of the color process, Figure 31 is a graph showing the relative transmittance of a particular contrast enhancement layer as a function of time when exposed to a particular amount of light. Fourth
The figure shows the transmittance of the maximum level J5 and the small level of transmittance for the image 1 of the last image 1, and thereby the transmittance of the CP
A set of graphs showing the instant IJ:'l]n1-las1-J3 and the integral con1~ras1~ as a function of human radiation, Figure 5 is related to the graph in Figure 4. Figures 6A to 6E represent the relative transmittance as a function of the amount of transmitted light. In the figure, 311 is the board, 32 is small 1 to resist 1 to lX;
, 33 Uha'n (-sis 1 to 11'1 strong layer, 354 to CIJ area, 36 to non-lighting area 1, deshi U38.39 to J, hi 40 to small 1 to resis) The coin purse part is shown.
99・“Jmu'fit!!far!Hitojineral・Satoshiku 1~Ric Cambai Agent (7630)
Living ? rii 11mi ni lvZwa 3 j〃r4

Claims (1)

[Claims] 1. A photoresist layer having a predetermined contrast threshold is sensitive to a photoresist layer having a contrast threshold less than the predetermined contrast threshold by use of a predetermined wavelength of light. and a method of producing a pattern during the resist day in which the projection image of the object with the transparent region to the right is formed, and the contrast of the projected image is avoided. (B) preparing the subject; (C) exhibiting sensitivity to light of the predetermined wavelength; The extinction coefficient 7 particle weight ratio in the IS two color state is greater than about 10 in β/2・■ units, and the ratio of the extinction coefficient in J3 in the non-bleached state and the extinction coefficient in the IBJ color state is greater than about 10. A second thick layer of a material capable of photobleaching containing a photo-182 dichroic compound is provided between the substrate and the photoresist layer and adjacent to the surface of the photoresist layer. (D) If light of the predetermined wavelength and a constant intensity is projected onto the photobleachable material layer for a predetermined period of time through the object, the photobleachable material layer will reflect the predetermined wavelength incident thereon. shows a decrease in optical density that is directly proportional to the amount of light, so that the integral contrast of the object that is transmitted by the light 1112 color-capable material layer increases with the amount of light transmitted thereby; reaching a maximum value and then decreasing, said maximum value of integrated contrast being set to be greater than a threshold value to said predetermined=1n] to las 1, and also depending on the sensitivity of said photoresist layer and said first thickness. The value of F91 is such that the amount of light transmitted by the photodecolorizable material layer within the F91 predetermined range completely exposes the resist layer from the small 1 to the resist layer and shows the transmitted image from the predetermined con 1 to las 1 to the threshold value. The subject is exposed to the subject for a sufficient period of time such that the amount of light within the predetermined range is transmitted through the photobleachable material layer under conditions set to provide a large contrast of 1-6 minutes. Through-C Projecting the light of the predetermined wavelength, and then (0) removing the photobleachable material layer to reveal the resist layer 11-1, resulting in a low contrast 1-image of the subject. A method characterized in that an IC no<turn with enhanced contrast is obtained in the small resist layer compared to C. , the ratio of the extinction coefficient of the photobleachable compound in the non-bleached state d3 to the extinction coefficient J'3 in the bleached state is greater than about 30 1'J
The method described in item 1 of the scope of n'1 items. 3. A patent in which the photobleachable compound is a compound selected from aryl-heron compounds [Claim 9 Nema No. 1]
1! ! Method described. 4. Said)'Lylni 1-[1-based compounds or α-(4-
4. The method of claim 3, wherein the wavelength of the predetermined wavelength is about 405 nm. 5. The 1j method according to claim 1, wherein the photodecolorizable material VF layer is in contact with the photoresist layers. 6. The method of claim 5, wherein the thickness of each layer of photoresist 1 is less than about 3 microns, and the thickness of the layer of colorable material is less than about 1 micron. 7. (A> Prepare a light source in a predetermined wavelength band; (B) prepare a photosensitive material layer having a first thickness containing a photosensitive material sensitive to light in the predetermined wavelength band; C) disposing a film having a transparent part and an opaque part between the light source and the photosensitive material layer; a second thickness of a photobleachable material layer having the property of reducing the amount of light absorbed by the film and the photosensitive material layer; The value of the sensitivity and the second thickness of the colorable material layer is such that the light 1]f2 of the image transmitted by the colorable material layer is determined by the predetermined wavelength band that is transmitted by it. The sensitivity of the photosensitive material layer to the predetermined wavelength band and the first thickness are set to increase with the amount of light (1 is the sensitivity of the photosensitive material layer to the predetermined wavelength band) and The substance capable of photobleaching is formed under conditions set such that the light end within a predetermined range transmitted by the substance layer is exposed to the photosensitive substance layer.
111 from the light source for a sufficient distance 111 to transmit light 11 within the predetermined range to the photosensitive material layer through the
A photosensitive material layer comprising steps of applying light of a certain intensity to the light 1j) (color TiJD material layer J3J) through the film 1a and the photosensitive material layer. 8. Forming an enhanced image of =1 contrast in the photosensitive material layer by developing the photosensitive material layer. 9T al'l search range No. 73 that includes two culms
h method described in f4. 9. The photosensitive material 'iH'
- Certain characteristics: the method according to item 7; 10. Non-IB2 (!2 state where the extinction coefficient/molecular weight ratio is 1!/Tusk/CTI single Il'C ゛ greater than about 10 and d3 into the non-nss color state and the extinction coefficient and l1l) color state The ratio of the extinction coefficient of light to a3 is greater than about 10. 9] h method described in jI. 11. The light 1112 Non-1j of the chromatic compound; the extinction coefficient/molecular weight ratio in the two-color state is greater than about 100, and the light 1j; the non-IBJ color of the monochromatic compound The ratio of the extinction coefficient in the J5 state to the extinction coefficient in the decolorized state is approximately 3.
Claim 10 greater than 0] h method described in J'm. 12. (A) Generate an aerial image of light in a predetermined wavelength band that passes through various strong marks, and (B) generate a G-light appendage sensitive to light in the predetermined wavelength band. (C) having a property that the amount of light absorbed in the predetermined wavelength band decreases in accordance with the amount of incident light in the predetermined wavelength band; a second thickness of photobleachable material layer of 1
11j between the aerial image and the photosensitive material layer, and then (D>the value of the sensitivity d5 and the second thickness of the material layer capable of one light and two colors is 1) θ arrangement Light 1j (of the image transmitted through the colorable material layer) is set to increase with the increase of the light in the predetermined wavelength band transmitted by the last layer, and the light 1j; The sensitivity J3 of the photosensitive material layer in the predetermined wavelength band J3 is the value of the first thickness J3: the amount of light within the predetermined range that passes through the colorable material layer J. The light 111 is set to expose the photosensitive material layer to the light within the predetermined range. 1) applying light from the aerial image for a sufficient period of time to transmit an amount of light; 13. A method of forming an image with enhanced contrast in a photosensitive material layer, characterized in that it consists of various structures.13. A contrast enhancement layer is disposed between the aerial image and the photosensitive material (v) 1 layer, and the contrast enhancement layer d3 and the photosensitive material are 14. A method characterized in that the contrast enhancing layer is also sensitive to light in a constant wavelength band.
S i constant wave ((having a characteristic that the absorption amount of light in the predetermined wavelength band decreases depending on the amount of light in the band,
The sensitivity and thickness 8 of the enhancement 11'1 are equal to the =1 ntrus l-
The enhancement layer is set such that the contrast of the transmitted image increases with the amount of light in the predetermined wavelength band transmitted thereby, and the predetermined wavelength of the photosensitive material layer In the band, the sensitivity of 45 degrees is set so that the amount of light transmitted through the contrast enhancement layer within a predetermined range exposes the photosensitive material waste!1. 13. The method of claim 1311J. 15. The method of claim 13, wherein the contrast enhancement layer is adjacent a surface of the photosensitive material layer. 16. The method of claim 13, wherein the contrast enhancement layer is adjacent to a surface of the photosensitive material layer. 14. The method according to item 13, wherein: light) j: a material layer capable of one color; 17. Photosensitivity 4! 1] payment according to claim 15), wherein the I material layer is the 1-regime 1 layer. 18. The light 11; the light IB dichroic compound in which the dichroic material layer is sensitive to light in the constant wavelength band 1. Method. 1. The method according to claim 18, wherein the photobleaching compound is an arylnitrone. 20. The photobleaching compound is α-(4-diethylaminophenyl)-N-phenylnitrone. The patent ij
``Law) as stated in the 19th JO during the 11th period of the request. 21. The above-mentioned light j1) The extinction coefficient/molecular suspension ratio of J3 in the non-bleached state of the dichroic compound is 1! /? J・Cm instep approximately 10
22. The absorption coefficient of the light + j + X color 111 compound in the non-1151! /J method according to claim 2111, in which the ratio is about 10 J, and the ratio is about 10 J;
3 [Noru light absorption 1 thread number/molecular weight ratio p/7・cm 41i
and the ratio of the extinction coefficient of the arylnitrone to the non-11 (J5 LJ in the chain state and the extinction coefficient of J>4J in the ++b color state is about 10 or more. 19 ]) 1 No. 2/1. Non-1j (extinction coefficient of a hub in the one-color state is larger than 7p/l-σ); non-11; extinction coefficient of J5 in the one-color state is Light 1 characterized by containing a compound selected from arylnitrone type compounds having a ratio to the coefficient of greater than about 10.
1) (color ii J ability 190 25, patent containing binder + jl'! sought range No. 24
10. The photobleachable layer according to 10. 26, (A>100 parts by weight (D a' uM solvent, (B
) 1 to 30 parts by weight of an inert polymeric binder; 27. α-(4-diethylaminophenyl)-N-phenylnitrone, α-(4-diethylaminophenyl)-
N-(4-chloro')1nyl)nido[, -1n, α-(
7I-diethylaminophenyl)-N-(3,4-cyclol'phenyl)nido1-1, α-(4-diethyltunominophenyl)-N-(4-11-xycarbonylphenyl)21-1 -1 nitrone, α-(4-diethylaminophenyl)-N-(4-acetylphenyl)nitrone, α-
(9-Uc1lysinyl)-N-phenylnitrone, α-
(9-10 Lysinyl)-N-(4-chlorophenyl)nitrone, α-(4-dimethylaminophenyl)-N-(
4-cyano2-1-nyl)nitrone, α-(4-meth1-xifinyl)-N-(4-cyanofuconyl)nide 1"
α-L2-(1-)1-benyl)1-N-
centre". N-7-[-L! YJ, Sujha is characterized by falling, Jtsu0
An aryl compound having an absorption maximum within the range of 0 to 450 nm. 28, Compound (x-(4-di-earthylaminofluor)
-N-F1-Flunitron. 2), compound (χ-(4-cytothylaminophyl)
-N-(/i-ri('lof'nyl)21-L'n. 1") upper nil) 21-1
1 n. 31, compound tx-(4-cyJ tylaminyl)-
1', I-<4-11 hexical small diruf'nyl)-1
-un. 32, compound α-(4-di-engineered tylaminof'-nyl)-
N-(4-ahitylph'-nyl)21-0. 33, compound α-(9-11'lycinyl)-N-phenylnide 1]n. 34, Compound α-(9-eurolidinyl)-N-(4-chloro1'Fyl)21~[-1n]. 35, compound α-(4-dimethyl7minophenyl)-N
-('ll-cyanotunyl)-l-r-+n. 36, compound α-(4-meth-1-1 diphenyl)-N-(
4-cyanoI-ru)21-11. 37, compound α-12-(1-71ylpropenyl m1
-N-phenylnide 11. 38, Compound α-12-(1,1-diphenyl-1-ranyl)]-N-f'-nil-[1-n.