CN101517485A - Method of forming a lithographic structure using a developer-trimmed hard mask - Google Patents

Abstract

The present invention provides novel developer-soluble hardmask compositions and methods of forming microelectronic structures using the hardmask compositions. The composition comprises a compound in a solvent system, wherein the compound is used for controlling the development rate and a cross-linking agent. The method includes applying the composition to a substrate such that the composition cures. An imaging layer is applied to the composition, followed by exposure and development, during which the exposed portions of the imaging layer, as well as portions of the hardmask composition adjacent to the exposed portions, are removed. The size of the hardmask composition structures is controlled by the development rate, and the resulting feature size is a fraction of the imaging layer feature size, resulting in a pattern that can ultimately be transferred to a substrate.

Description

Form the method for photolithographic structures with developer-trimmed hard mask

Background of invention

Related application

The application requires the right of priority of No. the 60/826th, 875, the provisional application that is entitled as " using developer-trimmed hard mask to form the method for photolithographic structures " submitted on September 25th, 2006, and its content is incorporated into this by reference.

Invention field

The present invention relates to the novel hard mask compositions that dissolves in developer widely, and uses this hard mask compositions to form the method for structure on semiconductor chip.

Description of the Prior Art

Higher current densities is sought by integrated circuit (IC) chip manufacturers constantly, the method for making sort circuit is being challenged the limit of photoetching technique always.Be the maturation of ArF technology in the most important achievement of this one side in recent years, and the exploitation of immersion photolithography.

The effort of these technology all is based on the most basic principle of optical physics, and promptly the resolution of image projected is directly proportional with the numerical aperture of projection lens and the inverse of incident wavelength.But, for the cost of utilizing these principles to improve resolution is significantly reducing of depth of focus (DOF).

DOF is with deciding photolithographic severe degree, thus the actual sexual factor of the productive rate of decision resulting devices.In order to remedy the loss of DOF, must reduce the thickness of photoresist.Unfortunately, in the individual layer technology of routine, photoresist thickness reduce to exist the limit.This limit by etch depth and photoresist to the choice of substrate decision.In the last few years, the etching selectivity of ArF photoresist had obtained significant raising, and was simultaneously, then very little to the further raising based on the photoresist of organic polymer.

For the reason of etching selectivity, people have explored many new photoetching processes, and for example bilayer or multilayer technology reduce photoresist thickness.It is to carry out photoresist by isotropic etching to cut method that the another kind that can adopt is selected.Cut the ability that method (trimming process) reduces characteristic dimension and can exceed photolithographic limit of power, for example cutting line may be very important for making transistor gate with the speed that improves device.But this technology has two basic defectives.At first, photoresist pattern not only edge laterally cuts, but also vertically cuts.By and large, vertical etch rate (etch rate) reaches as high as three times of lateral etch rate usually.Therefore, in cutting technology, quite a large amount of photoresist thickness losses of strict design have fallen.Secondly, cut plasma and will cause etching to following layer inevitably.Thisly do not wish that the etching that occurs sometimes may be very violent.

Summary of the invention

Composition and the method for the present invention by the novelty that does not have above-mentioned defective is provided overcome these problems of prior art.The present invention includes the composition that can be used as hard mask layer.Said composition comprises:

(B) comprise at least one-compound of OH group;

(ii) crosslinking chemical; And

(D) dicyandiamide solution, wherein (A), (B) and (C) be dissolved in or be scattered in the described dicyandiamide solution.The present invention also provides and has used this hard mask compositions that dissolves in developer with other to form the method for the microelectronic structure with nano-scale feature (feature).At last, the invention still further relates to the structure that forms by these methods.

Brief Description Of Drawings

Fig. 1 is the synoptic diagram that shows an embodiment of the inventive method;

Fig. 2 is the synoptic diagram that shows another embodiment of the present invention that uses the double patterning method;

Fig. 3 is scanning electron microscopy (SEM, 200KX) figure that is presented at the xsect of the wafer of testing among the embodiment 2;

Fig. 4 is SEM (200KX) figure that is presented at the xsect of the wafer of testing among the embodiment 3;

Fig. 5 is the SEM figure that is presented at the xsect of the wafer of testing among the embodiment 4;

Fig. 6 is SEM (150KX) figure that is presented at the xsect of the wafer of testing among the embodiment 5;

Fig. 7 is SEM (200KX) figure that is presented at the xsect of the wafer of testing among the embodiment 7.

Detailed description of the preferred embodiment

The present invention relates to and can in the process of making microelectronic component, be used as the composition of the novelty of hard mask, and the method for using the novelty of described hard mask.Said composition preferably comprises:

Wherein M is selected from Ti and Zr, and each R is independently selected from hydrogen and alkyl (alkyl of branching or non-branching, preferably about C ₁-C ₁₂Alkyl, more preferably from about C ₁-C ₆Alkyl).In a particularly preferred embodiment, R is selected from hydrogen ,-CH ₃With-C ₃H ₇(can be available from E.I.Du Pont Company (DuPont), commodity are by name

).

General assembly (TW) in described composition is 100 weight %, and said composition preferably comprises the compound of the formula (I) of about 1-20 weight %, more preferably from about the compound of the formula of 2-15 weight % (I), the more preferably from about compound of the formula of 3-10 weight % (I).More particularly, be 100 weight % in total weight of solids, the content of the compound of formula (I) should make the content of M be about 5-40 weight %, more preferably from about 10-30 weight %.

Except the compound of formula (I), described composition is preferably gone back inclusion compound (II), and this compound (II) comprises at least one group that can form covalent bond with the M of top formula (I).Preferred these groups comprise-OR ¹, R wherein ¹Be selected from hydrogen and alkyl (alkyl branching or non-branching, preferably about C ₁-C ₁₂Alkyl, more preferably from about C ₁-C ₆Alkyl).In a particularly preferred embodiment, these groups are selected from-OH and-OC ₂H ₅

This compound (II) should be an electron level, should stablize in hard mask formulation.That is to say that described compound should keep at least about 30 days in solution under the ambient storage condition (being 20-25 ℃).

Control is very important to this compound (II) for developing rate.That is to say, when the consumption of this compound is higher, will make composition, and the consumption of this compound will make the composition that has than slow development speed lower the time with very fast developing rate.Those of ordinary skills can regulate the amount of compound, so that obtain required developing rate when carrying out special process.Meanwhile, be 100 weight % in the general assembly (TW) of composition, the content of described compound is about 0.1-1 5 weight % usually, is more preferably 0.2-10 weight %, is more preferably 0.2-2 weight %.

In one embodiment, this compound (II) can also comprise the optical attenuation part of selecting to be used for to absorb the light of required wavelength.Can select these parts, be about the light of 400-10 nanometer with absorbing wavelength, the example of suitable light absorption part comprises benzyl rings.A kind of preferred described compound of the present invention (II) that is used for has following structural formula:

Composition of the present invention preferably also comprises crosslinking chemical.Preferred cross-linking agents comprises and is selected from following those: amino plastics, glycoluril (glycouril) and epoxy resin, wherein amino plastics most preferably.Particularly preferred crosslinking chemical is available from Sai Teke Industrial Co., Ltd (Cytec Industries Inc.), and trade mark is

General assembly (TW) in described composition is 100 weight %, and the content of crosslinking chemical preferably is about 0.1-15 weight % in the described composition, is more preferably 1-10 weight %, is more preferably 1-5 weight %.

If necessary, described composition can also comprise a large amount of optional components.The example of suitable optional component comprises the component that is selected from surfactant and adhesion promotor.In one embodiment, preferred described composition does not contain (be content approximately less than 0.1 weight %, preferably be about 0 weight %) any catalyzer substantially.Catalyzer comprise Photoacid generators (photoacid generator) and any other can be by heating or exposure and initiated polymerization or crosslinked reagent.Therefore, described composition preferably non-photosensitivity (promptly when described composition to about 1J/cm ²Radiant exposure the time, can not in layer, form pattern).

More than all these components all be dispersed or dissolved in the dicyandiamide solution.The boiling point that is used for the dicyandiamide solution of described hard mask compositions should be about 100-300 ℃, preferably is about 120-200 ℃.General assembly (TW) in described hard mask compositions is 100 weight %, and the consumption of described dicyandiamide solution should be about 70-98 weight %, preferably is about 80-95 weight %.Preferred dicyandiamide solution is organically, comprises being selected from following solvent: propylene glycol propyl ether, methyl isoamyl ketone, two (ethylene glycol) dimethyl ether, 3-ethoxyl ethyl propionate, propylene glycol monomethyl ether, ethyl lactate, cyclohexanone, and their potpourri.

In Fig. 1, shown method of the present invention, substrate 10 is provided in Figure 1A.Substrate 10 can be the microelectronic substrates of any routine, comprises being selected from following those: silicon, monox, silicon nitride, silicon oxynitride, aluminium, tungsten, tungsten silicide, gallium arsenide, germanium, tantalum, tantalum nitrite and SiGe.Substrate 10 has upper surface 12 and lower surface 14, in the embodiment shown, has the etching stopping layer 16 adjacent with lower surface 14.

For example above-mentioned hard mask compositions is applied over the upper surface 12 of substrate 10, forms hard mask layer 18 with upper surface 20.Described composition can apply by any known method of application, and preferred method of application is the described composition of spin coating under the rotating speed of about 1000-3000rpm, and preferred rotating speed is about 1,500-2,500rpm, the spin coating duration is about 10-90 second, preferably is about 20-60 second.In addition, although the embodiment shown in Figure 1A has shown layer 18 and has been applied directly on the upper surface 12 of substrate 10, but be to be understood that, can between substrate 10 and layer 18, introduce the optional middle layer (anti-reflecting layer for example of any amount, low k dielectric layer, silicon nitride layer, carbon film), layer 18 is applied on the middle layer of the top.

Can apply the back bake operation to what layer 18 was chosen wantonly then, desolvate to remove.Apply the back bake operation usually under about 80-160 ℃ temperature, more preferably under about 100-140 ℃ temperature, carry out about 10-60 second, more preferably about 20-40 second.Then layer 18 is cured and cures, usually cure bake more preferably from about under 175-185 ℃ the temperature, is carried out about 30-90 second under about 160-200 ℃ temperature, more preferably about 40-60 second.

In this cure bake process, the component interreaction in the hard mask layer 18 forms cured layer.As in the embodiment of hard mask compositions, between the component chemical reaction will take place at above-mentioned composition, form and be selected from following key:

And their potpourri, wherein the definition of M and R is same as above.Think crosslinking chemical can with the reaction of the compound of formula (I), but self-crosslinking can take place in crosslinking chemical, also may with compound (II) reaction, occupy by (III) and " matrix (matrix) " interior space of (IV) forming.

The thickness of the layer 18 that solidifies usually is about the 20-120 nanometer, is more preferably the 30-70 nanometer.In preparing with the embodiment that antireflection character is provided to layer 18, the k value of layer under the wavelength of about 400-10 nanometer of curing is at least about 0.1, preferably is about 0.2-0.6.The n value of layer under the wavelength of about 400-10 nanometer of solidifying is at least about 1.0, preferably is about 1.5-2.0.

The layer 18 that solidifies is insoluble to conventional photoresist solvent substantially.Therefore, when peeling off test, the layer 14 peel off percentage approximately less than 5%, preferably, be more preferably 0% approximately less than 1%.Peel off test and comprise the thickness (getting the mean value of the measured value of five different positions) of at first measuring the layer that solidifies.This is initial average film thickness.Next, and solvent (ethyl lactate for example, PGME, PGMEA) about 20 seconds of puddle on the film that solidifies, then about 2,000-3, the about 20-30 of centrifugal drying second is with except that desolvating under the rotating speed of 500rpm.Use ellipsometry five different point measurement thickness on wafer, obtain the mean value of these measured values.This is average final film thickness.

The amount of peeling off is the difference between initial average film thickness and the final average film thickness.Peeling off percentage is:

After layer 18 solidifies, imaging layer or photoresist (being photosensitivity) composition are applied on the upper surface 20 of layer 18, form imaging layer 22 with upper surface 24.Described photoetching compositions can be any commercially available photoresist, can select according to used wavelength.Photoresist applies (for example about 1,500-2 applies about 60 seconds under the rotating speed of 500rpm) by spin-coating method usually, but can adopt any known method of application.Then layer 22 is cured, under about 80-120 ℃ temperature, cure usually.These conditions only are exemplary rotating speed, spin coating time, stoving temperatures and cure the time.Those of ordinary skills can select these variablees, and/or can follow photoetching compositions manufacturer's suggestion.

The thickness of described imaging layer 22 after curing preferably approximately less than 100 nanometers, more preferably from about less than 50 nanometers, is more preferably the 20-40 nanometer usually approximately less than 250 nanometers.In addition, although the embodiment shown in Figure 1A has shown imaging layer 22 is applied directly on the upper surface 20 of hard mask layer 18, but be to be understood that, can have the listed above optional middle layer of any amount between imaging layer 22 and hard mask layer 18, imaging layer 22 is applied in above the middle layer of the top.

The mask (not shown) is set at above the surface 24 of imaging layer 22, will have the light directive mask of required wavelength, and described mask has opening, and described open design is used for making that light therefrom passes through, and contacts with the surface 24 of imaging layer 22.Those skilled in the art can understand at an easy rate, and the setting of opening is based on imaging layer 22, hard mask layer 18 and the final required pattern that forms and designs in substrate surface 12.Method of the present invention can use wavelength to be about the ultraviolet light of 400-10 nanometer, and still most preferably wavelength is 13.5 nanometers, 157 nanometers, 193 nanometers, 248 nanometers and 365 nanometers.

In the time of exposure, the part of the exposure of imaging layer 22 reacts, and makes these parts become and dissolves in developer.Preferably, hard mask layer 18 just dissolved in developer before exposure, still kept dissolving in developer after exposure.In this article, expression can be removed by these developers basically with the part that water developer, for example tetramethylammonium hydroxide and the KOH developer of routine contact " to dissolve in developer ".After the alkali developer with tetramethylammonium hydroxide (TMAH is generally 0.26N) and/or KOH (30-40% usually) and so on contacted 40 seconds, at least about 95%, preferably at least about 99%, more preferably from about 100% described part was removed by these developers.

Therefore, after exposure, imaging layer 22 contacts with the developer of hard mask layer 18 with TMAH or KOH developer and so on.According to the required degree (parts transversely that is included in imaging layer 22 remainders below is removed hard mask layer 18) of removing hard mask layer 18 of special process, described developer contact procedure can (for example be flooded by conventional method, puddle, spraying) carry out the different time.In general, the about 20-60 of developer contact second, more preferably from about 35-45 second.In this contact process, developer can be removed the exposed portion of imaging layer 22, and the part of the hard masking layer below these exposed portions 18, stays opening 26.Opening 26 can be hole, groove, interval etc., is transferred to the most at last on the substrate 10.Use the developer of TMAH and KOH developer and so on, with the speed of about 0.5-10 nm/sec, more preferably from about the speed of 1-3 nm/sec is removed hard mask layer 18.

After the contact developer, T shape structure 28 is retained on the surface 12 of substrate 10, perhaps is positioned on the middle layer arbitrarily on the surface 12.Why form T shape structure 28 and be because hard mask layer 18 dissolves in developer, the lateral etches of layer 18 can occur at the unexposed area of imaging layer 22, along with the developer prolongation of duration of contact, etched amount increases.

T shape structure 28 comprises the section 32 of upright shank 30 and cardinal principle level.The chemical constitution of shank 30 is identical with hard mask layer 18 after curing, comprises the top 34 and the bottom 36 that are linked to each other by opposing vertical sidewall 38a, 38b.Sidewall 38a, 38b are parallel to each other basically, also substantially perpendicular to substrate surface 12, can have bottom part 36 surface in contacts 12 on surface 12, perhaps can have middle layer arbitrarily on surface 12.That is to say that the angle " A " that vertical sidewall 38a or 38b and substrate surface 12 form is about 70 ° to 110 °, is more preferably 80 ° to 100 °, is more preferably 85 ° to 95 °.

The chemical constitution of section 32 with cure after imaging layer 22 identical, comprise corresponding upper surface 40a and lower surface 40b, and end wall 42a, 42b.Upper surface 40a and lower surface 40b are parallel to each other substantially, and are parallel to surface 12, and end wall 42a, 42b are parallel to each other substantially and be parallel to sidewall 38a, and 38b is simultaneously also substantially perpendicular to surface 12.The lower surface 40b of section 32 is adjacent with the top part 34 of shank 30.

Shown in Figure 1B, shank 30 has the width " W " that records from maximum distance position between vertical sidewall 38a, the 38b.Preferably, this method can be by regulating development time as mentioned above, thereby control " W " makes that " W " is less, can the overall height to shank 30 not cause any loss in etching process or in other operating process simultaneously.Method of the present invention can obtain approximately " W " less than 70 nanometers, preferably approximately less than 50 nanometers, more preferably from about less than 40 nanometers.

Section 32 has length " L ", promptly along the distance of maximum on the plane that is basically parallel to " W ".In some applications, " W " is approximately equal to " L ".Yet in preferred embodiment, " W " is less than " L ".In these embodiments, " W " be equal to or less than " L " 80%, be more preferably the 40-60% of " L ".In addition, shown in Figure 1B, T shape structure 28 has overall height " H ", and it is defined as from substrate surface 12 to section the ultimate range 32 the upper surface 40a.Preferably " H "/" W " is about 2-5, is more preferably 3-4.Therefore, the reducing of live width surpasses the live width of finishing with imaging layer 22, obtained being better than the significant advantage of prior art.

Shown in Fig. 1 C, use organic solvent (for example commercially available edge bead remover or soak into solvent in advance) to remove remaining imaging layer 22 (form of section 32) usually, stay the layer 44 of patterning.Referring to Fig. 1 D, the method (for example etching) by routine to substrate 10, forms the substrate 46 of patterning with the design transfer of the layer 44 of patterning.Described hard mask layer 18 (form of shank 30) has extremely low etch-rate, and etch-rate is much smaller than the etch-rate to substrate.That is to say that the etch-rate of hard mask layer 18 less than 1/3 of the etch-rate of conventional substrate 10 (for example silicon chip, metal substrate, polymer film), preferably approximately less than 1/10, more preferably from about less than 1/25, is more preferably the latter's 1/40 to 1/100 approximately.For the etchant of routine, comprise HBr, chlorine and oxygen etchant, like this really.Structure shown in Fig. 1 D can be used for further manufacturing step, for example metallization.

Preferably, the present invention can also adopt the double patterning method, thereby resulting resolution is improved twice or more times.This method is shown in Fig. 2, uses identical numbering at all embodiments that are used for similar material.Fig. 2 A is identical with Fig. 1 C, has shown the structure shown in Fig. 1 C to be used as the part of double patterning method, rather than has been used for method shown in Figure 1.That is to say that the structure of Fig. 1 C/2A has been passed through coating, photoetching and development, can apply once more now, photoetching and development, with further generation pattern.Come 2B with the aid of pictures below, shank 30 at first preferably hardens and cures.This sclerosis bake operation is preferably about at least 210 ℃, about 30-90 second under 220-280 ℃ the temperature more preferably from about, more preferably from about 30-60 second.Also available light is hardened according to replacing curing, and perhaps also carries out illumination outside curing, thereby makes it sclerosis.

Next, apply hard mask compositions, form second hard mask layer 48 with upper surface 50.Because layer 18 solidifies, shank 30 is hardened then, enforcement second coating step under the intact situation of the shank that therefore can form before keeping 30.The composition application step can be similar to step shown in Figure 1.In addition, people usually use the hard mask compositions identical with the embodiment of Fig. 1, but and do not require so, if necessary, can use different compositions.Can adopt and the identical condition of curing mentioned above, can obtain similar thickness and etch-rate.Can also on upper surface 50, form imaging layer or photoresist layer 22 as mentioned above.

At Fig. 2 C, the mask (not shown) that will have the required pattern of formation described herein is arranged on the surface 24 of imaging layer 22, repeats exposing operation mentioned above.Formed again the part of exposure in imaging layer 22, it is contacted with developer, the part with the hard mask layer 18 below the part after the part after the exposure of removing layer 22 and these exposures stays opening 52.These openings 52 can be hole, groove or interval.Formed identical T shape structure 28, it has and identical architectural feature mentioned above and character.For example with an organic solvent remove section 32 then once more, stay the structure shown in Fig. 2 D.The part of staying the projection on the substrate surface 12 shown in Fig. 2 D or shank 30 (similar with the described shank of Fig. 1 30) are commonly called line or protruding features.Hole, groove, at interval, the pattern of line and protruding features is transferred to substrate 10 the most at last.

Above-mentioned coating, cure, expose, development and imaging layer remove step and can repeat as required arbitrarily repeatedly, thereby form specific pattern in substrate surface 12.The structure of Fig. 2 C is carried out the operation of remaining step mentioned above, thereby design transfer is arrived substrate 10.Substrate to patterning carries out further manufacturing step (for example metallization) then.

Embodiment

Following examples have been described according to the preferred method of the present invention.Yet should be understood that these embodiment are illustrative, should not regard restriction as entire scope of the present invention.

Embodiment 1

Dissolve in the hard mask formulation I of developer

The component of said preparation is listed in table 1.According to following order, under stirring condition, raw material is mixed:

BTP, ethyl acetoacetate, solvent, 1303LF; And 2-cyano group-3-(4-hydroxy phenyl)-ethyl acrylate.This potpourri passes through 0.1 micron membrane filtration, to remove degranulation.Final preparation, carries out following two steps then and cures: cured 30 seconds at 120 ℃, cured 60 seconds at 180 ℃ then, make the film of 70 nanometers ± 5 nanometers to silicon wafer spin coating 40 seconds with the rotating speed of 2000rpm.The speed of described film with 5 nm/sec ± 1 nm/sec is dissolved among the TMAH of 0.26-N.Film is 1.6 ± 0.05 in the refractive index (being the n value) of 193 nanometers, is 1.8 ± 0.05 in the refractive index of 248 nanometers, is 1.7 ± 0.05 in the refractive index of 365 nanometers.Film is 0.44 ± 0.05 at the extinction coefficient (being the k value) of 193 nanometers, is 0.42 ± 0.05 at the extinction coefficient of 248 nanometers, is 0.40 ± 0.05 at the extinction coefficient of 365 nanometers.

Table 1: hard mask formulation I

^ is 100 weight % in the general assembly (TW) of all components in the composition.

Embodiment 2

The hard mask that the developer that is used in combination with the KrF photoresist cuts

The hard mask compositions that dissolves in developer that embodiment 1 is made is spin-coated on 200 millimeters the silicon wafer.Described hard mask layer is on hot surface, and heat curing is 60 seconds under 205 ℃ temperature.The thickness of the hot mask layer that dissolves in developer of described heat curing is 70 nanometers.(UV210 is available from (the Rohm ﹠amp of Rhom and Hass with commercially available KrF photoresist with ethyl lactate; Haas)) be diluted to the sixth (1/6) of initial solids content.Be applied on the hard mask layer by the photoresist of spin-coating method with dilution, forming thickness is the photoresist film of 50 nanometers.The wafer that comprises all films cured 60 seconds at 130 ℃, cured as after applying (PAB).Wafer is on SVGL/ASML Microscan III (0.6NA), to the wavelength exposure of 248 nanometers then.Post exposure bake (PEB) carried out 90 seconds at 130 ℃.Wafer uses the tetramethylammonium hydroxide (TMAH) of 0.26N to develop 60 seconds.Fig. 3 has shown the line image of gained.The width of the hard line image that grinds is 42 nanometers.

Embodiment 3

The hard mask that the developer that is used in combination with the ArF photoresist cuts

The hard mask compositions that dissolves in developer that embodiment 1 is made is spin-coated on 200 millimeters the silicon wafer.This hard mask is on hot surface, and 205 ℃ of heat curings 60 seconds, the thickness of the hard mask film that dissolves in developer of this heat curing was 40 nanometers.By spin-coating method commercially available ArF photoresist (TArF-Sa-103 is available from TOK) is applied on the hard mask, forming thickness is the film of 250 nanometers.The wafer that comprises all films cured 60 seconds at 110 ℃, cured as after applying (PAB).Wafer (0.75NA and 0.89/0.65 ∑) on ASML PASS5500/1100 scanner exposes under the wavelength of 193 nanometers then.At 110 ℃ of PEB that carry out 60 seconds.Wafer uses the tetramethylammonium hydroxide (TMAH) of 0.26N to develop 60 seconds.Fig. 4 has shown the line image of gained.The width of the line image of the hard mask of gained is 66 nanometers.

Embodiment 4

Dissolve in the hard mask formulation II of developer

The component of said preparation is listed in Table II.According to following order, under stirring condition, raw material is mixed: solvent;

AA-105,

1135; And 2-cyano group-3-(4-hydroxy phenyl)-ethyl acrylate.This potpourri passes through 0.1 micron membrane filtration, to remove degranulation.Final preparation, carries out following two steps then and cures: cured 30 seconds at 120 ℃, cured 60 seconds at 180 ℃ then, make the film of 40 nanometers ± 5 nanometers to silicon wafer spin coating 40 seconds with the rotating speed of 2000rpm.Film is dissolved among the TMAH of 0.26N with the speed of 3 nm/sec ± 1 nm/sec.Film is 1.6 ± 0.05 in the refractive index of 193 nanometers, is 1.8 ± 0.05 in the refractive index of 248 nanometers, is 1.7 ± 0.05 in the refractive index of 365 nanometers.Film is 0.39 ± 0.05 at the extinction coefficient of 193 nanometers, is 0.37 ± 0.05 at the extinction coefficient of 248 nanometers, is 0.48 ± 0.05 at the extinction coefficient of 365 nanometers.

The hard mask formulation II of Table II

^ is 100 weight % in the general assembly (TW) of all components in the composition.

Hard mask formulation II is spin-coated on the silicon wafer of 200-millimeter, described film is on hot surface, 120 ℃ of heat curings 40 seconds, then 180 ℃ of heat curings 60 seconds.The hard mask that dissolves in developer of heat curing is the film of 40 nanometer thickness.By spin-coating method commercially available ArF photoresist (TAI6016 is available from TOK) is applied on the hard mask, forming thickness is the film of 120 nanometers.The wafer that comprises all films cured 60 seconds at 120 ℃, cured as after applying (PAB).Wafer (0.75NA and 0.89/0.59 ∑) on ASML PASS5500/1100 scanner exposes under the wavelength of 193 nanometers then.At 110 ℃ of PEB that carry out 60 seconds.Wafer uses the tetramethylammonium hydroxide (TMAH) of 0.26N to develop 60 seconds.Fig. 5 has shown the line image of gained.The condition of this embodiment is optimized unlike embodiment 2 and 3, and explanation can obtain to improve by optimization.

Embodiment 5

Dissolve in the hard mask formulation III of developer

The component of said preparation is listed in Table III.According to following order, under stirring condition, raw material is mixed: solvent;

AA-105, 1135; And 2-cyano group-3-(4-hydroxy phenyl)-ethyl acrylate.This potpourri passes through 0.1 micron membrane filtration, to remove degranulation.Final preparation, carries out following two steps then and cures: cured 30 seconds at 120 ℃, cured 60 seconds at 180 ℃ then, make the film of 40 nanometers ± 5 nanometers to silicon wafer spin coating 40 seconds with the rotating speed of 2000rpm.Film is dissolved among the TMAH of 0.26N with the speed of 2 nm/sec ± 1 nm/sec.Film is 1.6 ± 0.05 in the refractive index of 193 nanometers, is 1.8 ± 0.05 in the refractive index of 248 nanometers.Film is 0.45 ± 0.05 at the extinction coefficient of 193 nanometers, is 0.44 ± 0.05 at the extinction coefficient of 248 nanometers.

Table III: hard mask formulation III

^ is 100 weight % in the general assembly (TW) of all components in the composition.

Hard mask formulation is spin-coated on the silicon wafer of 200-millimeter, described hard mask film is on hot surface, 120 ℃ of heat curings 40 seconds, then 170 ℃ of heat curings 60 seconds.The hard mask that dissolves in developer of heat curing is the film of 40 nanometer thickness.By spin-coating method commercially available ArF photoresist (TAI6016) is applied on the hard mask, forming thickness is the film of 120 nanometers.The wafer that comprises all films cured 60 seconds at 120 ℃, cured as after applying (PAB).Wafer (0.75NA and 0.89/0.59 ∑) on ASML PASS5500/1100 scanner exposes under the wavelength of 193 nanometers then.At 110 ℃ of PEB that carry out 60 seconds.Wafer uses the tetramethylammonium hydroxide (TMAH) of 0.26N to develop 60 seconds.Fig. 6 has shown the line image of gained.The condition of this embodiment is optimized unlike embodiment 2 and 3, and explanation can obtain to improve by optimization.

Embodiment 6

Dissolve in the hard mask formulation IV of developer

The component of said preparation is listed in Table IV.According to following order, under stirring condition, raw material is mixed: solvent;

AA-105, and 2-cyano group-3-(4-hydroxy phenyl)-acrylic acid ethyl ester.This potpourri passes through 0.1 micron membrane filtration, to remove degranulation.Final preparation, carries out following two steps then and cures: cured 30 seconds at 120 ℃, cured 60 seconds at 180 ℃ then, make the film of 40 nanometers ± 5 nanometers to silicon wafer spin coating 40 seconds with the rotating speed of 2000rpm.Film is dissolved among the TMAH of 0.26N with the speed of 2 nm/sec ± 1 nm/sec.Film is 1.6 ± 0.05 in the refractive index of 193 nanometers, is 1.8 ± 0.05 in the refractive index of 248 nanometers.Film is 0.49 ± 0.05 at the extinction coefficient of 193 nanometers, is 0.49 ± 0.05 at the extinction coefficient of 248 nanometers.

Table IV. hard mask formulation IV

^ is 100 weight % in the general assembly (TW) of all components in the composition.

Embodiment 7

Dissolve in the hard mask formulation V of developer

The component of said preparation is listed in Table V.Will in the reactor of cooling device is housed

BTP and 2, the 4-pentanedione mixes, and forms intermediate.In this exothermal reaction process, the temperature of reactor remains on room temperature.This intermediate at first with solvent, under stirring condition, add remaining component then.This potpourri passes through 0.1 micron membrane filtration, to remove degranulation.Final preparation, carries out following two steps then and cures: cured 30 seconds at 120 ℃, cured 60 seconds at 180 ℃ then, make the hard mask film of 77 nanometers ± 5 nanometers to silicon wafer spin coating 40 seconds with the rotating speed of 2000rpm.Film is dissolved among the TMAH of 0.26N with the speed of 4 nm/sec ± 1 nm/sec.Film is 1.6 ± 0.05 in the refractive index of 193 nanometers, is 1.8 ± 0.05 in the refractive index of 248 nanometers, is 1.7 ± 0.05 in the refractive index of 365 nanometers.Film is 0.39 ± 0.05 at the extinction coefficient of 193 nanometers, is 0.38 ± 0.05 at the extinction coefficient of 248 nanometers, is 0.41 ± 0.05 at the extinction coefficient of 365 nanometers.

Table V: hard mask formulation V

^ is 100 weight % in the general assembly (TW) of all components in the composition.

Hard mask formulation is spin-coated on 200 millimeters the silicon wafer, described hard mask film is on hot surface, 120 ℃ of heat curings 40 seconds, then 180 ℃ of heat curings 60 seconds.The hard mask that dissolves in developer of heat curing is the film of 40 nanometer thickness.By spin-coating method commercially available ArF photoresist (TAI6016) is applied on the hard mask, forming thickness is the film of 120 nanometers.The wafer that comprises all films cured 60 seconds at 120 ℃, cured as after applying (PAB).Wafer (0.75NA and 0.89/0.59 ∑) on ASML PASS5500/1100 scanner exposes under the wavelength of 193 nanometers then.At 110 ℃ of PEB that carry out 60 seconds.Wafer uses the tetramethylammonium hydroxide (TMAH) of 0.26N to develop 60 seconds.Fig. 7 has shown the line image of gained.

Claims (24)

1. A composition useful as a hard mask layer, said composition comprising:

In the formula: M is selected from Ti and Zr; each R is independently selected from hydrogen and alkyl; (B) compounds comprising at least one -OH group; (C) a crosslinking agent; and (D) A solvent system wherein (A), (B) and (C) are dissolved or dispersed in said solvent system. 2. The composition of claim 1, wherein the compound (B) further comprises an alkoxy group. 3. The composition of claim 1, wherein the crosslinking agent is an aminoplast crosslinking agent. 4. A method of forming a microelectronic structure, said method comprising: applying a first composition to a microelectronic substrate, or to an intermediate layer on said microelectronic substrate, forming a hard mask thereon mold layer. The first composition comprises:

In the formula: M is selected from Ti and Zr; each R is independently selected from hydrogen and alkyl; (B) compounds comprising at least one -OH group; (C) a crosslinking agent; and (D) A solvent system wherein (A), (B) and (C) are dissolved or dispersed in said solvent system. 5. The method of claim 4, further comprising applying an imaging layer to the hardmask layer, or to an intermediate layer on the hardmask. 6. The method of claim 5, further comprising selectively exposing the imaging layer to light having a wavelength of about 400-10 nanometers to form exposed portions of the imaging layer. 7. The method of claim 6, further comprising contacting the imaging layer and the hard mask layer with a developer after the exposing such that the exposed portion, and the Portions of the hard mask layer adjacent to the exposed portions are removed by the developer to form a patterned layer. 8. The method of claim 7, further comprising: (a) baking the patterned layer; (b) applying a second composition to the patterned layer, forming a second hard mask layer on the patterned layer. 9. The method of claim 8, further comprising: (c) baking the second hard mask layer; (d) applying an imaging layer to said second hard mask layer; (e) exposing said imaging layer to form exposed portions in said imaging layer; (f) contacting the exposed portion with a developer to remove the exposed portion and the portion of the hard mask layer adjacent to the exposed portion from the substrate to form a second patterned layer . 10. The method of claim 9, further comprising: optionally repeating steps (b)-(e) one or more times; transferring the pattern of the patterned layer to a substrate. 11. The method of claim 10, wherein the transferring step includes etching the patterned layer and substrate. 12. A microelectronic structure comprising: a microelectronic substrate having a surface, the substrate having an etch rate; and A T-shaped structure on the surface of the substrate or on an intermediate layer on the surface of the substrate, the T-shaped structure comprising: an upstanding leg comprising a hard mask having an etch rate, the leg having upper and lower portions connected by opposing vertical sidewalls substantially perpendicular to the substrate surface, said lower portion is in contact with said substrate surface or intermediate layer; and A generally horizontal section, which includes the imaging layers, having the following characteristics: adjacent to the upper portion, or adjacent to an intermediate layer on the upper portion; and Substantially perpendicular to the vertical sidewalls, the hard mask etch rate is at least about three times the substrate etch rate. 13. The structure of claim 12, wherein said legs have a maximum distance measured between said vertical side walls: a width "W"; said horizontal sections have a length "L", It is the maximum distance along a plane generally parallel to "W", which is approximately equal to or less than 80% of "L". 14. The structure of claim 12, wherein: the horizontal section has an upper surface; said T-shaped structure has a height "H" defined as the maximum distance from said substrate surface to said upper surface; said legs have a width "W" defined as the maximum distance between said vertical side walls; "H"/"W" is about 2-5. 15. The structure of claim 12, wherein the vertical sidewalls and the substrate surface form an angle of about 80-100[deg.]. 16. The structure of claim 12, wherein the hard mask comprises a structure selected from the group consisting of:

and mixtures thereof, wherein: M is selected from Ti and Zr; each R is independently selected from hydrogen and alkyl. 17. The structure of claim 12, wherein the microelectronic structure is selected from the group consisting of silicon, silicon oxide, silicon nitride, silicon oxynitride, aluminum, tungsten, tungsten silicide, gallium arsenide, germanium, tantalum , Tantalum Nitrite and SiGe. 18. A microelectronic structure comprising: a microelectronic substrate having a surface, and A T-shaped structure on the surface of the substrate or on an intermediate layer on the surface of the substrate, the T-shaped structure comprising: an upstanding leg comprising an upper portion connected by opposing vertical side walls and a lower portion, the lower portion being in contact with either the substrate surface or the intermediate layer, the vertical side walls and the substrate the surfaces form an angle of about 80-100°; and A generally horizontal segment having the following properties: adjacent to the upper portion, or adjacent to an intermediate layer on the upper portion; and generally perpendicular to the vertical side walls. 19. The structure of claim 18, wherein the upright legs comprise a structure selected from the group consisting of:

and mixtures thereof, wherein: M is selected from Ti and Zr; each R is independently selected from hydrogen and alkyl. 20. The structure of claim 18, wherein the microelectronic structure is selected from the group consisting of silicon, silicon oxide, silicon nitride, silicon oxynitride, aluminum, tungsten, tungsten silicide, gallium arsenide, germanium, tantalum , Tantalum Nitrite and SiGe. 21. The structure of claim 18, wherein said legs have a maximum distance measured between said vertical side walls: a width "W"; said horizontal sections have a length "L", It is the maximum distance along a plane generally parallel to "W", which is approximately equal to or less than 80% of "L". 22. The structure of claim 18, wherein: the horizontal section has an upper surface; said T-shaped structure has a height "H" defined as the maximum distance from said substrate surface to said upper surface; said legs have a width "W" defined as the maximum distance between said vertical side walls; "H"/"W" is about 2-5. 23. A method of forming a microelectronic structure, the method comprising: providing a microelectronic substrate having a surface optionally including one or more intermediate layers thereon, the substrate having an etch rate; applying a hardmask composition to the surface of the substrate, or to an intermediate layer on the surface of the substrate, thereby forming a hardmask layer thereon, the hardmask layer having an etch rate such that the etch rate of the hard mask is at least about three times the etch rate of the substrate; optionally forming one or more intermediate layers on the hard mask layer; forming an imaging layer on the hard mask layer, or on an intermediate layer on the hard mask; exposing the imaging layer to form an exposed portion of the imaging layer; After exposure, developing the imaging layer to remove the exposed portions, and portions of the hard mask layer adjacent to the exposed portions, the developing step is on the substrate surface, or Forming a T-shaped structure on the intermediate layer on the surface of the substrate, the T-shaped structure comprising: An upright leg comprising an upper portion and a lower portion connected by opposing vertical side walls, the vertical side walls being generally perpendicular to the substrate surface, the lower portion being in contact with the substrate surface or the intermediate layers are in contact; and A generally horizontal segment having the following properties: adjacent to the upper portion, or adjacent to an intermediate layer on the upper portion; and generally perpendicular to the vertical side walls. 24. A method of forming a microelectronic structure, the method comprising: providing a microelectronic substrate having a surface optionally including one or more intermediate layers thereon; applying a hardmask composition to the surface of the substrate, or to an intermediate layer on the surface of the substrate, to form a hardmask layer thereon; optionally forming one or more intermediate layers on the hard mask layer; forming an imaging layer on the hard mask layer, or on an intermediate layer on the hard mask; exposing the imaging layer to form exposed portions in the imaging layer; After exposure, developing the imaging layer to remove the exposed portions, and portions of the hard mask layer adjacent to the exposed portions, the developing step is on the substrate surface, or Forming a T-shaped structure on the intermediate layer on the surface of the substrate, the T-shaped structure comprising: An upright leg comprising an upper portion and a lower portion connected by opposing vertical side walls, the vertical side walls being generally perpendicular to the substrate surface, the lower portion being in contact with the substrate surface or the intermediate layer is in contact, the vertical sidewalls and the substrate surface form an angle of about 80-100°; and A generally horizontal segment having the following properties: adjacent to the upper portion, or adjacent to an intermediate layer on the upper portion; and generally perpendicular to the vertical side walls.

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