CN103187245B - Method of photoetching of block copolymer through directed self-assembly - Google Patents
Method of photoetching of block copolymer through directed self-assembly Download PDFInfo
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- CN103187245B CN103187245B CN201110456341.6A CN201110456341A CN103187245B CN 103187245 B CN103187245 B CN 103187245B CN 201110456341 A CN201110456341 A CN 201110456341A CN 103187245 B CN103187245 B CN 103187245B
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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Abstract
The invention provides a method of photoetching of a block copolymer through directed self-assembly. The method of photoetching of the block copolymer through directed self-assembly comprises the steps of forming a side wall on a side wall surface of an isolation interval area of a photoetching pattern, using the photoetching pattern and the side wall to serve as masking film to irradiate the surface of a phenylethyltrichlorosilane (PETS) layer so as to form a chemical pattern, reducing the width of a chemical modification area in the chemical pattern, coating the block copolymer on the surface of the PETS layer with the chemical pattern in a spin mode, forming a self-assembly layer, carrying out annealing, and combining chemical guidance directed self-assembly (DSA) and morphology guidance DSA to form a periodic structure domain.
Description
Technical field
The present invention relates to a kind of semiconductor making method, particularly a kind of photoetching method by directed self-assembled block copolymers.
Background technology
Along with the development of semiconductor technology, existing photoetching technique can not adapt to the structure manufacture on nano-scale.There is self assembly (self-assembly, SA) self-assembled film of characteristic is divided into self-assembled monolayer (self-assembly monolayer by its membrane formation mechanism, and LBL self assembly film (Layer by layer self assembled membrane) SAM), the current research to high polymer Macromolecular self-assembly field is mainly for liquid crystal polymer, block copolymer, the polymer of key or hydrogen bond and the combination of oppositely charged system can be formed, the wherein SAM of block copolymer, because its self assembly characteristic is that patterning on nano-scale provides another approach.For diblock copolymer, after substrate surface spin coating diblock copolymer, microphase-separated by forming the polymer of diblock copolymer (such as, by implementing thermal annealing when the glass transition temperature higher than described polymer or being annealed by solvent) after annealing is spontaneously assembled into two kinds of polymer blocks combinations with periodic structure.But the periodic structure of this polymer blocks combination is not a kind of ordered domains, as shown in Figure 1.Therefore directed self assembly (Directed self-assembly is proposed in order to form ordered domains (well-organized structures) on nano-grade size, DSA) block copolymer technology, thus provide another approach for the patterning carrying out photoetching on nano-scale.DSA can be divided into pattern to guide DSA and chemistry to guide DSA according to its principle.Wherein, chemistry guides DSA to compare pattern and guides the advantage of DSA to be, can provide longer ordered domains, and realize arranging more accurately.
Composition graphs 3 ~ 9 illustrates that in prior art as shown in Figure 2, chemistry guides the photolithography process figure of DSA block copolymer, and its concrete steps are as follows:
Step 201, Fig. 3 is the cross-sectional view that in prior art, chemistry guides the lithography step 201 of DSA block copolymer, as shown in Figure 3, deposition on wafer phenylethyltrichlorosilane (phenylethyltrichlorosilane, PETS) layer 302.
In the context of subject application, term " semiconductor substrate " or " semiconductive substrate " or " semiconductive wafer fragment " or " wafer fragment " or " wafer " are interpreted as the arbitrary structure meaning to comprise semi-conducting material (including but not limited to bulk semiconductive materials), such as, semiconductor wafer (separately or it comprises the component of other material) and semiconductive material layers (separately or comprise the sub-assembly of other material).Term " substrate " refers to arbitrary supporting structure, includes but not limited to above-mentioned semiconductive substrate, wafer fragment and wafer.
Substrate in this step is described for wafer, and described wafer has silicon substrate 300 (substrate), deposited silicon dioxide layer 301 in the wafer device side of silicon substrate 300, at the surface deposition PETS layer 302 of described silicon dioxide layer 301.The step of deposition PETS layer 302 is prior art, repeats no more.
Step 202, Fig. 4 is the cross-sectional view that in prior art, chemistry guides the lithography step 202 of DSA block copolymer, as shown in Figure 4, PETS layer 302 applies photoresist, and after photoetching, described photoresist patterned forms photoengraving pattern 403.
In this step, photoetching refers to that exposure and development form the step of photoengraving pattern 403, and this step is prior art, repeats no more.It should be noted that, photoengraving pattern 403 defines the array of raceway groove arranged in parallel, each raceway groove has following structure: sidewall and bottom surface, wherein, the length of raceway groove is several times as much as the width of its bottom surface, and part PETS layer exposes as the bottom surface of raceway groove, and part photoresist forms spacer interval between raceway groove, visible, the sidewall of spacer interval i.e. the sidewall of raceway groove.The width of trench floor and the width sum of spacer interval define chemistry and guide the DSA cycle (Ls), and Ls is subject to the accuracy limitations of photoetching technique.
Step 203, Fig. 5 is the cross-sectional view that in prior art, chemistry guides the lithography step 203 of DSA block copolymer, as shown in Figure 5, for mask, PETS layer 302 is irradiated with photoengraving pattern 403, form chemical pattern (chemical pattern) on PETS layer 302 surface.
In this step, irradiation is irradiated PETS layer 302 by extreme ultraviolet light (EUV) known in the art, X ray or electron beam (E-bearn) exposure system under oxygen atmosphere.For the part PETS layer 302 do not covered by photoengraving pattern 403, with oxygen generation chemical reaction under above-mentioned light beam or electron beam irradiation, make it by nonpolar chemical modification (Chemically modified) region 501 of changing polarity into, its width is w; Then do not had and oxygen generation chemical reaction by another part PETS layer 302 that photoengraving pattern 403 covers, still keep nonpolar state, be called on-chemically modified (Non-Chemically modified) region 502.
Step 204, Fig. 6 is the cross-sectional view that in prior art, chemistry guides the lithography step 204 of DSA block copolymer, as shown in Figure 6, stripping photolithography pattern 403.
In this step, stripping photolithography pattern 403 can with dry etching or wet etching.
Step 205, Fig. 7 is the cross-sectional view that in prior art, chemistry guides the lithography step 205 of DSA block copolymer, as shown in Figure 7, at the surperficial spin coating diblock copolymer of the PETS layer 302 with chemical pattern as SAM.
The present embodiment is described for poly-(styrene-b-methyl methacrylate) (PS-b-PMMA) 701 of diblock copolymer.
The film form (comprising the size and shape of microphase-separated domains) controlling patterned film in prior art by the molecular weight of different polymer blocks and volume fraction in adjustment block copolymer is to produce sheet, cylinder or the form such as spherical.For example, ratio for two blocks (polymer A and polymer B) of diblock polymer is greater than the volume fraction of about 80:20, block copolymer can microphase-separated be self-assembled into periodic spherical domains, and wherein the matrix of polymer A surrounds the matrix of polymer B.For the ratio of two blocks between the situation about between 60:40 and 80:20, described diblock copolymer is assembled into the cylinder of polymer B in polymer A matrix of periodically hexagon closs packing or honey-comb shape array.For between the ratio about between 50:50 and 60:40, lamellar domains or the alternating stripes of described block can be formed.
Step 206, Fig. 8 is the cross-sectional view that in prior art, chemistry guides the lithography step 206 of DSA block copolymer, as shown in Figure 8, diblock copolymer is annealed, its self assembly forms two kinds of polymer blocks combinations, and two kinds of polymer blocks combinations are the ordered domains with periodic structure.
In this step, the domain cycle (L of polymer blocks combination
0) satisfy condition L
0during=Ls, because chemistry guides the polarity of DSA to select, two kinds of polymer blocks combinations can form the ordered domains with periodic structure.Wherein, the chemical modification region 501 of described polarity will guide PMMA preferential wetting, form the PMMA block (PMMA block) 801 of strip above it, in the nonpolar on-chemically modified region 502 presenting neutral wetting state, according to the characteristic of diblock copolymer, PS will form the PS block (PS block) 802 of strip centered by PMMA matrix on the on-chemically modified region 502 of its both sides.
Step 207, Fig. 9 is the cross-sectional view that in prior art, chemistry guides the lithography step 207 of DSA block copolymer, and as shown in Figure 9, a kind of polymer blocks of selective removal, forms patterned film 901.
After DSA, optionally remove a kind of polymer blocks such as PMMA block 801, using the patterned film 901 formed as etch mask.Due to the domain cycle (L of polymer blocks involved in the method combination
0) be determined by the molecular chain length of block copolymer (MW), the definition of the patterned film 901 therefore formed is better than such as by other technology such as photolithographies, and simultaneously the cost of described DSA block copolymer photoetching technique is well below the cost of the electron beam lithography or EUV lithography technology with suitable definition.
From above-mentioned steps, the chemistry of prior art guides DSA formation to have the polymer blocks combination of the ordered domains of periodic structure, and the patterned film that formed of certain polymer blocks of follow-up removal is subject to the restriction of lithographic accuracy, so also limited to the characteristic size of patterned film.
Summary of the invention
In view of this, the technical problem that the present invention solves is: in the photoetching method of the directed self-assembled block copolymers that chemistry guides, the patterned film that formed after the ordered domains with periodic structure that polymer blocks is formed and certain polymer blocks of follow-up removal, is subject to the lithographic accuracy restriction of photoengraving pattern.
For solving the problem, technical scheme of the present invention is specifically achieved in that
By a photoetching method for directed self-assembled block copolymers, a substrate is provided, described substrate deposits PETS layer, described PETS layer applies photoresist, after photoetching, described photoresist patterned forms photoengraving pattern, and described photoengraving pattern comprises spacer interval and the first raceway groove, and the method comprises:
Described photoengraving pattern surface deposition cover layer;
Cover layer described in dry etching forms side wall at the spacer interval sidewall of described photoengraving pattern;
With described photoengraving pattern and side wall for mask irradiates described PETS layer, form chemical pattern on described PETS layer surface, in described chemical pattern, the width in chemical modification region is less than the width of described first raceway groove;
Peel off described photoengraving pattern and side wall;
At the described PETS layer surface spin coating block copolymer with chemical pattern as Iy self-assembled layer;
After described annealing of substrates, Self-Assembling of Block Copolymer forms polymer blocks combination, and described polymer blocks combination is the ordered domains with periodic structure;
Remove certain polymer blocks and form patterned film.
Described cover layer is silicon dioxide, silicon nitride, N doping diamond dust, or amorphous carbon.
Described stripping photolithography pattern and side wall can with dry etching or wet etchings.
Described block copolymer is diblock copolymer, triblock copolymer or segmented copolymer.
Described diblock copolymer is poly-(styrene-b-methyl methacrylate) (PS-b-PMMA), polyethylene glycol oxide-polyisoprene, polyethylene glycol oxide-polybutadiene, polyethylene glycol oxide-polystyrene, polyethylene glycol oxide-polymethyl methacrylate, Polystyrene-Polyethylene base Pyrrolizidine, polystyrene-poly isoprene (PS-b-PI), polystyrene-polybutadiene, polybutadiene-polyvinylpyrrolidine pyridine or polyisoprene-polymethyl methacrylate; Described triblock copolymer is poly-(styrene-b methyl methacrylate-block-ethylene oxide).
Described annealing is carried out in carbon disulfide atmosphere.
The temperature range of described annealing is 100 to 300 degrees Celsius, and the time range of described annealing is 8 to 12 hours.
The domain period L that the bottom surface of described first raceway groove and the width sum Ls of described spacer interval and described polymer blocks combine
0relation meet nL
0=Ls, n are more than or equal to the integer that 2 are less than or equal to 10.
The width range in described chemical modification region is less than or equal to 60 nanometers.
As seen from the above technical solutions, the invention provides a kind of photoetching method by directed self-assembled block copolymers, the method forms side wall in the sidewall surfaces of photoengraving pattern, using photoengraving pattern and side wall as mask, the irradiates PETS layer surface and forms chemical pattern, thus reduce the width in the chemical modification region in described chemical pattern, then there is the PETS layer surface spin coating copolymer of chemical pattern and annealing; In annealing process, first guide DSA to form specific morphology at substrate surface based on chemistry, in non-chemical modification region, be then spontaneously assembled into the polymer blocks combination with periodic structure based on pattern guiding DSA; The follow-up polymer blocks by having periodic structure combines and obtains patterned film, the method overcomes the lithographic accuracy restriction of photoengraving pattern, adds pattern density and the precision of the patterned film formed by the photoetching of directed self-assembled block copolymers.
Accompanying drawing explanation
Fig. 1 is the periodic structure schematic diagram of the polymer blocks combination of non-ordered domains in prior art;
Fig. 2 is the photolithography process figure that in prior art, chemistry guides DSA block copolymer;
Fig. 3 ~ 9 are the cross-sectional view that in prior art, chemistry guides the photoetching of DSA block copolymer;
Figure 10 is the photolithography process figure of the specific embodiment of the invention one DSA block copolymer;
Figure 11 ~ 19 are the cross-sectional view of the photoetching of the specific embodiment of the invention one DSA block copolymer.
Embodiment
For making object of the present invention, technical scheme and advantage clearly understand, to develop simultaneously embodiment referring to accompanying drawing, the present invention is described in more detail.
The present invention proposes a kind of photoetching method by directed self-assembled block copolymers, the method forms side wall in the sidewall surfaces at photoengraving pattern, irradiate PETS layer surface using photoengraving pattern and side wall as mask and form chemical pattern, thus reduce the width in the chemical modification region in described chemical pattern, then there is the PETS layer surface spin coating copolymer of chemical pattern and annealing, thus first guide DSA after substrate surface forms specific morphology based on chemistry, in non-chemical modification region, the polymer blocks combination with periodic structure is spontaneously assembled into again based on pattern guiding DSA, finally remove wherein certain polymer blocks and form patterned film.
Specific embodiment one
The photolithography process figure of DSA block copolymer of the present invention is as shown in Figure 10 described in conjunction with Figure 11 ~ 19, and its concrete steps are as follows:
Step 1001, Figure 11 is the cross-sectional view of the lithography step 1001 of DSA block copolymer of the present invention, as shown in figure 11, deposition on wafer phenylethyltrichlorosilane layer (PETS) 302.
In the context of subject application, term " semiconductor substrate " or " semiconductive substrate " or " semiconductive wafer fragment " or " wafer fragment " or " wafer " are interpreted as the arbitrary structure meaning to comprise semi-conducting material (including but not limited to bulk semiconductive materials), such as, semiconductor wafer (separately or it comprises the component of other material) and semiconductive material layers (separately or comprise the sub-assembly of other material).Term " substrate " refers to arbitrary supporting structure, includes but not limited to above-mentioned semiconductive substrate, wafer fragment and wafer.In the present embodiment, there is provided a wafer (wafer) as substrate, described wafer has silicon substrate (substrate) 300, and the wafer device side of silicon substrate 300 has silicon dioxide layer 301, at the surface deposition PETS layer 302 of described silicon dioxide layer 301.The step of deposition PETS layer 302 is prior art, repeats no more.It should be noted that can also deposit other semi-conducting materials on silicon substrate 300 replaces silicon dioxide layer 301, that is the present invention is including but not limited to the material surface deposition PETS layer 302 of silicon dioxide layer 301.
Step 1002, Figure 12 is the cross-sectional view of the lithography step 1002 of DSA block copolymer of the present invention, as shown in figure 12, PETS layer 302 applies photoresist, and after photoetching, photoresist patterned forms photoengraving pattern 403.
In this step, photoetching refers to that exposure and development form the step of photoengraving pattern 403, and this step is prior art, repeats no more.It should be noted that, photoengraving pattern 403 defines the array of the first raceway groove arranged in parallel, each first raceway groove has following structure: sidewall and bottom surface, part PETS layer exposes as the bottom surface of the first raceway groove, and part photoresist forms spacer interval between the first raceway groove, visible, the sidewall of spacer interval i.e. the sidewall of raceway groove.The width of the first trench floor and the width sum of spacer interval define the cycle (Ls) that chemistry guides DSA, Ls is determined by lithographic accuracy, so under the prerequisite not changing existing photoetching technique, the limiting value of Ls cannot change, it is identical with prior art with the length of step and Ls that concrete photoengraving pattern 403 forms method, repeats no more.
Step 1003, Figure 13 is the cross-sectional view of the lithography step 1003 of DSA block copolymer of the present invention, as shown in figure 13, photoengraving pattern 403 surface deposition cover layer 1301;
In this step, described cover layer 1301 can be silicon dioxide, silicon nitride, N doping diamond dust (NDC, Nitrogen Doped silicon Carbide) such as boron nitride (BN) and carbonitride of silicium (SiCN), or amorphous carbon, different according to the material of cover layer 1301, the deposition process of its correspondence is prior art, repeats no more
Step 1004, Figure 14 is the cross-sectional view of the lithography step 1004 of DSA block copolymer of the present invention, and as shown in figure 14, cover layer 1301 described in dry etching forms side wall 1401 at the spacer interval sidewall of photoengraving pattern 403.
In this step, because dry etching is anisotropy, thus remove be deposited on the top, spacer interval of photoengraving pattern 403 and the part of covering layer 1301 of trench bottom while can retain and be attached to part of covering layer on the sidewall of spacer interval thus form side wall 1401.Because the existence of side wall 1401 adds the width (area of isolation of photoengraving pattern 403 formation originally and side wall 1401 are simultaneously as area of isolation) of spacer interval, also just correspondingly the first channel width is reduced, such as by regulating the thickness of sedimentary cover 1301, by the width control system of the first raceway groove after reducing in 60 nanometers (nm) below.As everyone knows, the restriction of existing photoetching technique has reached the limit of the first channel width, the method that the present invention proposes utilizes the side wall 1401 formed to reduce the first channel width further, can overcome the restriction of the lithographic accuracy of photoengraving pattern 403 to the L of follow-up block copolymer
0restriction.Dry etching in this step can be plasma etching, and the relevant parameter of dry etching and the method for controlling stopping of dry etching are prior art, such as, according to thickness and the dry etching speed of cover layer 1301, controls the dry etching time; Or adopt endpoint detection method to control the stopping of dry etching.
Step 1005, Figure 15 is the cross-sectional view of the lithography step 1005 of DSA block copolymer of the present invention, as shown in figure 15, irradiates PETS layer, form chemical pattern on PETS layer surface with photoengraving pattern 403 and side wall 1401 for mask.
In this step, irradiation is irradiated PETS layer by extreme ultraviolet light (EUV) known in the art, X ray or electron beam (E-bearn) exposure system under oxygen atmosphere.For not by the part PETS layer that photoengraving pattern 403 and side wall 1401 cover, with oxygen generation chemical reaction under above-mentioned light beam or electron beam irradiation, make it by nonpolar chemical modification region 1501 of changing polarity into; Then do not had and oxygen generation chemical reaction by another part PETS layer that photoengraving pattern 403 and side wall 1401 cover, still keep nonpolar state, be called nonpolar non-chemical modification region 1502.
Because the first channel width formed in step 1103 and step 1104 reduces, correspondingly this step irradiate form chemical modification region 1501 width w compared to existing technology in the width in chemical modification region also can reduce.Particularly, the width of the first raceway groove formed after the width w in chemical modification region 1501 of the present invention is less than photoetching, the width w scope in chemical modification region of the present invention is less than or equal to 60 nanometers (nm).
Step 1006, Figure 16 is the cross-sectional view of the lithography step 1006 of DSA block copolymer of the present invention, as shown in figure 16, stripping photolithography pattern 403 and side wall 1401.
In this step, stripping photolithography pattern 403 and side wall 1401 can with dry etching or wet etchings, concrete, can with dry etching or wet etching stripping photolithography pattern 403 and side wall 1401 simultaneously, first dry method or wet etching can also be adopted to peel off side wall 1401, then the method for dry method or wet etching stripping photolithography pattern 403.
Step 1007, Figure 17 is the cross-sectional view of the lithography step 1007 of DSA block copolymer of the present invention, as shown in figure 17, has the PETS layer surface spin coating diblock copolymer of chemical pattern
The present embodiment is described for poly-(styrene-b-methyl methacrylate) (PS-b-PMMA) 1701 of diblock copolymer, but PETS layer is surperficial also can the block copolymer (i.e. triblock copolymer or segmented copolymer) of spin coating other types.The example of diblock copolymer mainly comprises poly-(styrene-b-methyl methacrylate) (PS-b-PMMA), polyethylene glycol oxide-polyisoprene, polyethylene glycol oxide-polybutadiene, polyethylene glycol oxide-polystyrene, polyethylene glycol oxide-polymethyl methacrylate, Polystyrene-Polyethylene base Pyrrolizidine, polystyrene-poly isoprene (PS-b-PI), polystyrene-polybutadiene, polybutadiene-polyvinylpyrrolidine pyridine or polyisoprene-polymethyl methacrylate.The example of triblock copolymer comprises poly-(styrene-b methyl methacrylate-block-ethylene oxide).
In this step, the chemical functional group (chemical functional group of such as PMMA) of corresponding block polymer is selected according to the width in chemical modification region, also just require that the length of this chemical functional group is consistent with the width in chemical modification region or conform to, concrete system of selection is prior art, repeats no more.Visible, because the width in chemical modification region of the present invention diminishes, result in the reduction of chemical functional group's length of the block polymer of selection, concerning the block copolymer with this block copolymer, the domain period L of polymer blocks combination
0also can correspondingly reduce.To the domain period L of the polymer blocks combination of the PS-b-PMMA 1701 that this enforcement is selected
0the domain cycle of the polymer blocks combination of PS-b-PMMA in prior art must be less than.When the ratio of two block polymers (polymer A: PS and polymer B: PMMA) in PS-b-PMMA is between about between 50:50 and 60:40 during volume fraction, the block copolymer combinations that PS-b-PMMA 1701 can be formed in subsequent annealing step is lamellar domains or alternating stripes.
Step 1008, the cross-sectional view of the lithography step 1008 that Figure 18 ~ 19 are DSA block copolymer of the present invention, as shown in Figure 18 ~ 19, annealing of wafer, diblock copolymer self assembly forms two kinds of polymer blocks combinations, and two kinds of polymer blocks combinations are the ordered domains with periodic structure.
In this step, wafer is put into carbon disulfide atmosphere (CS
2) anneal, the temperature range of annealing is 100 to 300 degrees Celsius (DEG C), such as 100 DEG C, 200 DEG C or 300 DEG C, and the time range of annealing is 8 to 12 hours, such as 8 hours, 10 hours or 12 hours.Can there be multiple combination concrete annealing temperature and time, such as: at 180 DEG C, carry out annealing in 10 hours, or at 150 DEG C, first carry out the first time annealing of 5 hours, at 200 DEG C, then carry out second time annealing in 5 hours.
In annealing process, be divided into following two stages for the self assembly of the diblock copolymer of PS-b-PMMA 1701:
The generalized section of first stage as shown in figure 18, first the compatibility of polarization state to PMMA that present of the chemical modification region on PETS layer surface is larger, so chemical modification region will preferentially be soaked by PMMA, form the PMMA block (PMMA block) 1801 of strip, nonpolar non-chemical modification region 1502 presents neutral wetting state simultaneously, because this neutral wetting state has equivalent compatibility to two of diblock copolymer kinds of polymer (PS/PMMA), and centered by PMMA matrix (PMMA block), the PS block (PS block) 1802 of strip will be formed in its both sides according to the performance polymer PS of diblock copolymer.
The generalized section of second stage as shown in figure 19, in the non-chemical modification region 1502 presenting neutral wetting state, the PMMA block 1801 that the first stage is formed and PS block 1802 forms the second raceway groove as spacer region on the surface in non-chemical modification region 1502.This second raceway groove has following structure: sidewall and bottom surface.Second raceway groove is equivalent to form substrate topography, guides the principle of DSA according to pattern, and the second raceway groove can affect the orientation of the microphase-separated domains of copolymer, sequence and alignment.In the present embodiment, the bottom surface of the second raceway groove is the part in non-chemical modification region 1502, and entropic force impels the neutral wetting surface in non-chemical modification region 1502 to be subject to the wetting of two kinds of polymer blocks of diblock copolymer, produces vertical orientated self assembly form; And the sidewall surfaces of the second raceway groove can be subject to the preferential wetting of the polymer (PS or PMMA) of a certain composition in block copolymer, thus the polymer blocks of strip during this content polymer self assembly, can be formed along the sidewall of the second raceway groove.Work as nL
0during=Ls, under chemistry guides DSA polarity to select and pattern guides DSA, be finally combined to form the ordered domains with periodic structure by PS and PMMA two kinds of polymer blocks.Wherein, Ls is the width sum of trench floor and spacer interval, L
0for the domain cycle of polymer blocks combination, n is more than or equal to the integer that 2 are less than or equal to 10.As shown in figure 18, in the present embodiment, diblock copolymer self assembly forms the periodic structure territory that two kinds of polymer blocks combinations are alternating stripes.
Step 1009, Figure 19 is the cross-sectional view of the lithography step 1009 of DSA block copolymer of the present invention, and as shown in figure 19, a kind of polymer blocks of selective removal, forms patterned film 1901.
In this step, removing specific a kind of polymer blocks concrete grammar is prior art, repeat no more, the patterned film 1901 optionally removing PMMA block 1801 formation in the present embodiment can be used as etch mask, be cover manufacturing structure in the substrate of below with this etch mask, be applied to the making such as the metal wire of such as grid and metal level.
Specific embodiment two
Specific embodiment two is identical with the step of specific embodiment one, but in the step of PETS layer surface spin coating diblock copolymer with chemical pattern, by adjusting the ordered domains with periodic structure of Self-Assembling of Block Copolymer formation and the film form of subsequent pattern film in the volume fraction proportional control annealing of wafer process between the block polymer forming block copolymer.Such as when the ratio of two block polymers (polymer A: PS and polymer B: PMMA) in PS-b-PMMA is between the situation about between 60:40 and 80:20, DSA is become the block copolymer combinations of periodically hexagon closs packing or honey-comb shape array by PS-b-PMMA, and wherein polymer B is the cylinder in polymer A matrix.Periodic cylindrical structures is parallel and grow perpendicular on the direction of substrate.Produce vertical cylindrical body by thermal annealing and require that base plate bottom is generally neutral wetting state to block copolymer.But by substrate surface chemical modification and after the size in chemical modification region being reduced, form the pattern in sparse chemical modification region on its surface.Subsequently, after block copolymer heating anneal, at the ad-hoc location of substrate surface, comprise the region of chemical modification region and non-chemical modification, formed and there is periodic cylindrical patterned film.The film of this patterning can be used as etch mask, is cover manufacturing structure in the substrate of below, is applied to the making such as the through hole of such as magnetic storage device, metal level with this etch mask.
Above-mentioned specific embodiment one and specific embodiment two visible, the present invention proposes a kind of photoetching method by directed self-assembled block copolymers, the sidewall surfaces of the method in the spacer interval of photoengraving pattern forms side wall and reduces channel dimensions, irradiate PETS layer surface using photoengraving pattern and side wall as mask and form chemical pattern, thus reduce the width in the chemical modification region in described chemical pattern, then anneal as Iy self-assembled layer at the PETS layer surface spin coating block copolymer with chemical pattern, guide DSA after substrate surface forms the specific morphology of polymer blocks combination based on chemistry, block copolymer in non-chemical modification region guides DSA to be spontaneously assembled into periodic structure territory based on pattern, finally remove wherein certain polymer blocks and form patterned film.The method overcome the lithographic accuracy restriction of photoengraving pattern, add pattern density and the precision of the patterned film formed by the photoetching of directed self-assembled block copolymers.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within the scope of protection of the invention.
Claims (9)
1. the photoetching method by directed self-assembled block copolymers, one substrate is provided, described substrate deposits phenylethyltrichlorosilane PETS layer, described PETS layer applies photoresist, after photoetching, described photoresist patterned forms photoengraving pattern, described photoengraving pattern comprises spacer interval and the first raceway groove, and it is characterized in that, the method also comprises:
Described photoengraving pattern surface deposition cover layer;
Cover layer described in dry etching forms side wall at the spacer interval sidewall of described photoengraving pattern;
With described photoengraving pattern and side wall for mask irradiates described PETS layer, form chemical pattern on described PETS layer surface, in described chemical pattern, the width in chemical modification region is less than the width of described first raceway groove;
Peel off described photoengraving pattern and side wall;
At the described PETS layer surface spin coating block copolymer with chemical pattern as Iy self-assembled layer;
After described annealing of substrates, Self-Assembling of Block Copolymer forms polymer blocks combination, and described polymer blocks combination is the ordered domains with periodic structure;
The polymer blocks removing the chemical modification overlying regions in polymer blocks combination forms patterned film.
2. method according to claim 1, is characterized in that, described cover layer is silicon dioxide, silicon nitride, N doping diamond dust, or amorphous carbon.
3. method according to claim 1, is characterized in that, described stripping photolithography pattern and side wall dry etching or wet etching.
4. method according to claim 1, is characterized in that, described block copolymer is diblock copolymer, triblock copolymer or segmented copolymer.
5. method according to claim 4, it is characterized in that, described diblock copolymer is poly-(styrene-b-methyl methacrylate), polyethylene glycol oxide-polyisoprene, polyethylene glycol oxide-polybutadiene, polyethylene glycol oxide-polystyrene, polyethylene glycol oxide-polymethyl methacrylate, Polystyrene-Polyethylene base Pyrrolizidine, polystyrene-poly isoprene, polystyrene-polybutadiene, polybutadiene-polyvinylpyrrolidine pyridine or polyisoprene-polymethyl methacrylate; Described triblock copolymer is poly-(styrene-b methyl methacrylate-block-ethylene oxide).
6. method according to claim 1, is characterized in that, described annealing is carried out in carbon disulfide atmosphere.
7. method according to claim 1, is characterized in that, the temperature range of described annealing is 100 to 300 degrees Celsius, and the time range of described annealing is 8 to 12 hours.
8. method according to claim 1, is characterized in that, the domain period L that the width sum Ls of described first trench floor and described spacer interval and described polymer blocks combine
0meet nL
0=Ls, n are more than or equal to the integer that 2 are less than or equal to 10.
9. method according to claim 1, is characterized in that, the width range in described chemical modification region is less than or equal to 60 nanometers.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110456341.6A CN103187245B (en) | 2011-12-30 | 2011-12-30 | Method of photoetching of block copolymer through directed self-assembly |
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| KR102394994B1 (en) | 2013-09-04 | 2022-05-04 | 도쿄엘렉트론가부시키가이샤 | Uv-assisted stripping of hardened photoresist to create chemical templates for directed self-assembly |
| US9793137B2 (en) | 2013-10-20 | 2017-10-17 | Tokyo Electron Limited | Use of grapho-epitaxial directed self-assembly applications to precisely cut logic lines |
| US9349604B2 (en) | 2013-10-20 | 2016-05-24 | Tokyo Electron Limited | Use of topography to direct assembly of block copolymers in grapho-epitaxial applications |
| KR20160084437A (en) | 2013-11-08 | 2016-07-13 | 에이에스엠엘 네델란즈 비.브이. | Methodology to generate a guiding template for directed self-assembly |
| KR102166523B1 (en) * | 2013-12-02 | 2020-10-16 | 에스케이하이닉스 주식회사 | Structure and Method of fabricating nano scale features and structure including the features |
| TWI546846B (en) * | 2014-05-16 | 2016-08-21 | 旺宏電子股份有限公司 | Patterning method and patterning apparatus |
| US9305834B1 (en) * | 2014-12-30 | 2016-04-05 | GlobalFoundries, Inc. | Methods for fabricating integrated circuits using designs of integrated circuits adapted to directed self-assembly fabrication to form via and contact structures |
| FR3031750B1 (en) * | 2015-01-21 | 2018-09-28 | Arkema France | PROCESS FOR OBTAINING THICK ORDERED FILMS AND HIGH PERIODS COMPRISING A BLOCK COPOLYMER |
| US9947597B2 (en) | 2016-03-31 | 2018-04-17 | Tokyo Electron Limited | Defectivity metrology during DSA patterning |
| WO2019190463A1 (en) * | 2018-03-26 | 2019-10-03 | Intel Corporation | Multifunctional molecules for selective polymer formation on conductive surfaces and structures resulting therefrom |
| CN110993565A (en) * | 2019-12-11 | 2020-04-10 | 成都工业学院 | Method for preparing semiconductor nano device structure by directional self-assembly |
| CN113448163B (en) * | 2020-03-25 | 2023-08-29 | 芯恩（青岛）集成电路有限公司 | DSA-based photoetching method |
| CN113496877B (en) * | 2020-04-01 | 2024-07-16 | 中芯国际集成电路制造(上海)有限公司 | Method for forming semiconductor structure |
| CN114551225A (en) * | 2020-11-25 | 2022-05-27 | 浙江大学 | Method for self-assembly photoetching of chiral-oriented block copolymer |
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