1. Field
Example embodiments relate to methods of forming a blocking pattern and to methods of manufacturing a semiconductor device including the same. More particularly, example embodiments relate to methods of forming a blocking pattern using a photosensitive composition and to methods of manufacturing a semiconductor device including the same.
2. Description of the Related Art
Generally, a capacitor may include a lower electrode, a dielectric layer, and an upper electrode, and may be employed in a memory device, e.g., a DRAM device. As a degree of integration of the memory device increases, an area of a unit cell including at least one capacitor in the memory device may decrease. In order to improve capacitance of the capacitor in a highly integrated memory device, e.g., a memory device having a gigabyte of data storage capacity, the capacitor may have a volumetric structure, e.g., a box type structure or a cylindrical type structure, having a high aspect ratio. For example, a cylindrical capacitor may include a lower electrode having a cylindrical shape.
The conventional lower electrode of the capacitor may include forming a mold layer pattern, forming a blocking pattern on the mold layer pattern, e.g., by a chemical vapor deposition (CVD) process or by using a photoresist, and forming the lower electrode. Once the lower electrode is formed, the blocking pattern and the mold layer pattern may be removed.
The conventional blocking pattern formed by a film deposition process, e.g., CVD, however, may include voids therein. Further, the blocking pattern formed by the film deposition process may not be sensitive to light, so an additional photolithography process may be required to form the blocking pattern in a specific region of the mold layer pattern.
The conventional blocking pattern formed by using a photoresist, however, may cause plasma damage to the lower electrode, when the blocking pattern is removed from the lower electrode by an ashing process. Further, portions of the photoresist may not be easily removed from the lower electrode by the ashing process when the photoresist is baked, so polymeric contaminants, i.e., portions of the photoresist, may remain on the lower electrode to cause defects in a semiconductor device.
Further, a conventional etching process for removing the mold layer pattern may shift, pull, or remove portions of the lower electrode. In particular, a conventional process of forming lower electrodes on the conventional mold pattern may include forming a portion of a lower electrode in an edge die region of a substrate, i.e., a peripheral portion of the substrate. As a result, an abnormal lower electrode may be formed in the edge die region of the substrate, and may be removed or shifted in a subsequent etching process, i.e., during removal of the mold layer pattern. Removal or shifting of the abnormal electrode may cause a defect in the semiconductor device.
Example embodiments are therefore directed to methods of forming a blocking pattern and methods of manufacturing a semiconductor device including the same, which substantially overcome one or more of the disadvantages of the related art.
It is therefore a feature of an example embodiment to provide methods of forming a blocking pattern using a photosensitive composition that may simplify a semiconductor manufacturing process.
It is another feature of an example embodiment to provide methods of forming a blocking pattern using a photosensitive composition that may reduce generation of defects in a semiconductor device.
It is yet another feature of an example embodiment to provide methods of manufacturing a semiconductor device using a blocking pattern with one or more of the above features.
At least one of the above and other features and advantages of the present invention may be realized by providing a method of forming a blocking pattern, including forming a preliminary blocking layer on first and second regions of a substrate, the preliminary blocking layer being formed of a photosensitive composition including a siloxane polymer, a cross-linking agent, a photoacid generator, and a thermal acid generator, selectively exposing to light a first portion of the preliminary blocking layer, the first portion of the preliminary blocking layer being formed on the first region of the substrate, such that a cross-linked pattern may be formed on the first region of the substrate, and removing a second portion of the preliminary blocking layer, the second portion of the preliminary blocking layer being formed on the second region of the substrate. The first region of the substrate may include an edge die region, and the second region of the substrate may include a die forming region.
The method may further include curing the preliminary blocking layer after removing the second portion of the preliminary blocking layer from the second region, curing the preliminary blocking layer including performing a thermal treatment process. Removing the second portion of the preliminary blocking layer may include completely removing the preliminary blocking layer from the second region of the substrate, such that only the cross-linked pattern on the first region of the substrate may be cured by the thermal treatment process. Removing the second portion of the preliminary blocking layer may include partially removing the preliminary blocking layer from the second region of the substrate to form a partial layer on the second region of the substrate, such that both the cross-linked pattern on the first region and the partial layer on the second region may be cured by the thermal treatment process. Removing the second portion of the preliminary blocking layer from the second region may be performed by a developing process. The photosensitive composition may be formed of about 0.1 parts to about 20 parts by weight of the cross-linking agent, about 0.01 parts to about 20 parts by weight of the photoacid generator, and about 0.01 parts to about 20 parts by weight of the thermal acid generator, based on about 100 parts by weight of the siloxane polymer. The photosensitive composition may be formed of a siloxane polymer including silicon-oxygen bonds in a backbone and at least one labile group substituent, the labile group being an acid-labile group and/or a heat-labile group.
At least one of the above and other features and advantages of the present invention may be realized by providing a method of forming a blocking pattern, including forming a pattern structure with openings on a substrate, the substrate including a die forming region and an edge die region, forming a preliminary blocking layer on the pattern structure to fill the openings, forming the preliminary blocking layer including coating a photosensitive composition on the pattern structure, the photosensitive composition including a siloxane polymer, a cross-linking agent, a photoacid generator, and a thermal acid generator, selectively exposing to light a first portion of the preliminary blocking layer to form a first preliminary blocking pattern on the pattern structure in the edge die region of the substrate, the first preliminary blocking pattern including a cross-linked portion, removing a second portion of the preliminary blocking layer, the second portion of the preliminary blocking layer being formed in the die forming region of the substrate, such that a second preliminary blocking pattern may be formed in the openings of the pattern structure in the die forming region of the substrate, and curing the first and the second preliminary blocking patterns to form a first blocking pattern in the edge die region and a second blocking pattern in the die forming region.
Forming the pattern structure on the substrate may include forming a layer on the substrate, forming a photoresist film on the layer, forming a photoresist pattern on the layer by performing an exposure process on the photoresist film using a first reticle, the first reticle defining a first reticle image corresponding to a first number of dies, and etching the layer using the photoresist pattern as an etching mask to form the pattern structure on the substrate. Selectively exposing to light the preliminary blocking layer may include using a second reticle, the second reticle defining a second reticle image corresponding to a second number of dies, and the second number of dies being larger than zero and smaller than the first number of dies.
At least one of the above and other features and advantages of the present invention may be realized by providing a method of manufacturing a semiconductor device, including forming at least one conductive structure on a substrate, the substrate including a die forming region and an edge die region, forming a mold layer pattern on the substrate, the mold layer pattern including at least one opening exposing the conductive structure, forming a conductive layer on sidewalls and a bottom of the opening and on an upper surface of the mold layer pattern, forming a preliminary blocking layer on the conductive layer to fill the opening, forming the preliminary blocking layer including coating a photosensitive composition on the conductive layer, the photosensitive composition including a siloxane polymer, a cross-linking agent, a photoacid generator and a thermal acid generator, selectively exposing to light a first portion of the preliminary blocking layer to form a first preliminary blocking pattern on the conductive layer in the edge die region of the substrate, the first preliminary blocking pattern including a cross-linked portion, removing a second portion of the preliminary blocking layer, the second portion of the preliminary blocking layer being formed in the die forming region of the substrate, such that a second preliminary blocking pattern may be formed in the opening of the mold layer pattern in the die forming region of the substrate, curing the first and the second preliminary blocking patterns by a thermal treatment process to form a first blocking pattern in the edge die region and a second blocking pattern in the die forming region, and removing a portion of the conductive layer in the die forming region to form at least one lower electrode in the die forming region.
The method may further include removing the first blocking pattern from the edge die region, and the mold layer pattern and the second blocking pattern from the die forming region, after forming the lower electrode in the die forming region. Removing the first and second blocking patterns and the mold layer pattern may be performed using a solution including hydrogen fluoride, ammonium fluoride and water. Forming the mold layer pattern on the substrate may include forming a mold layer on the substrate, forming a photoresist film on the mold layer, forming a photoresist pattern on the mold layer by performing an exposure process on the photoresist film using a first reticle defining a first reticle image corresponding to a first number of dies, and etching the mold layer using the photoresist pattern as an etching mask to form the mold layer pattern on the substrate. Selectively exposing to light the first portion of the preliminary blocking layer may be performed using a second reticle defining a second reticle image corresponding to a second number of dies, the second number of dies being larger than zero and smaller than the first number of dies. The thermal treatment process may be performed at a temperature of about 100° C. to about 300° C.
The above and other features and advantages of the present invention will become more apparent to those of ordinary skill in the art by describing in detail example embodiments thereof with reference to the attached drawings, in which:
FIGS. 23 and 24A-24C illustrate schematic diagrams of reticle images in accordance with example embodiments;
Korean Patent Application No. 10-2007-0081623, filed on Aug. 14, 2007, in the Korean Intellectual Property Office, and entitled: “Methods of Forming a Blocking Pattern Using a Photosensitive Composition and Methods of Manufacturing a Semiconductor Device,” is incorporated by reference herein in its entirety.
Example embodiments will now be described more fully hereinafter with reference to the accompanying drawings, in which exemplary embodiments of the invention are illustrated. Aspects of the invention may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
In the figures, the dimensions of layers, elements, and regions may be exaggerated for clarity of illustration. It will also be understood that when a layer or element is referred to as being “on” another layer, element, or substrate, it can be directly on the other layer, element, or substrate, or intervening layers and/or elements may also be present. Further, it will also be understood that when a layer or element is referred to as being “between” two layers or elements, it can be the only layer or element between the two layers or elements, or one or more intervening layers and/or elements may also be present. In addition, it will be understood that when an element is referred to as being “connected” or “coupled” to another element, it can be directly connected or coupled to the other element or intervening elements may be present. In contrast, when an element is referred to as being “directly connected” or “directly coupled” to another element, there are no intervening elements present. Like reference numerals refer to like elements throughout.
As used herein, the expressions “at least one,” “one or more,” and “and/or” are open-ended expressions that are both conjunctive and disjunctive in operation. For example, each of the expressions “at least one of A, B, and C,” “at least one of A, B, or C,” “one or more of A, B, and C,” “one or more of A, B, or C” and “A, B, and/or C” includes the following meanings: A alone; B alone; C alone; both A and B together; both A and C together; both B and C together; and all three of A, B, and C together. Further, these expressions are open-ended, unless expressly designated to the contrary by their combination with the term “consisting of.” For example, the expression “at least one of A, B, and C” may also include an nth member, where n is greater than 3, whereas the expression “at least one selected from the group consisting of A, B, and C” does not.
It will be understood that, although the terms first, second, third etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another region, layer or section. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the present invention.
The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the present invention. As used herein, the singular forms a, an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.
Example embodiments are described herein with reference to cross-sectional illustrations that are schematic illustrations of idealized example embodiments (and intermediate structures). As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, example embodiments should not be construed as limited to the particular shapes of regions illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, an implanted region illustrated as a rectangle will, typically, have rounded or curved features and/or a gradient of implant concentration at its edges rather than a binary change from implanted to non-implanted region. Likewise, a buried region formed by implantation may result in some implantation in the region between the buried region and the surface through which the implantation takes place. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the actual shape of a region of a device and are not intended to limit the scope of the present invention. In addition, as used herein, a “die” may also be a chip and “chip” may also be a die.
Unless otherwise defined, all terms including technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Method of Forming a Blocking Pattern
Referring to
The die forming region of the substrate 10 may be in a central portion of the substrate 10, e.g., a portion of the substrate 10 in which a complete semiconductor chip may be formed. The edge die region may be a peripheral portion of the substrate 10, and may surround the die forming region of the substrate 10. The edge die region may be smaller than the die forming region, so a complete semiconductor chip, e.g., a capacitor, may not be formed therein. In other words, a size of the edge die region of the substrate 10 may be insufficient to include a semiconductor chip therein.
The photosensitive composition for forming the preliminary blocking layer 12 may be formed as follows. The photosensitive composition may include a siloxane polymer, a cross-linking agent, a photoacid generator, and a thermal acid generator. The photosensitive composition may include about 0.1 parts to about 20 parts by weight of the cross-linking agent, about 0.01 parts to about 20 parts by weight of the photoacid generator and about 0.01 parts to about 20 parts by weight of the thermal acid generator, based on about 100 parts by weight of the siloxane polymer. The amounts of the components of the photosensitive composition may be adjusted in accordance with properties of the blocking pattern, the amount of acid generated by heat or light or a curing temperature.
The siloxane polymer of the photosensitive composition may be a polymer having silicon-oxygen bonds in a backbone and at least one labile group substituent, e.g., an acid-labile group substituent and/or a heat-labile group substituent. For example, the siloxane polymer may include a repeating unit represented by Formula 1 below,
where R1 may be a C1-C10 alkyl, a cycloalkyl, an aryl or a silylalkyl, each of which may have an acid-labile group and/or a heat-labile group. Non-limiting examples of the acid-labile and/or heat-labile group may include a —COOR3 ester, a —OCOOR4 carbonate, a —OR5 ether, an acetal, a ketal, etc. Non-limiting examples of R3 in the —COOR3 ester may include t-butyl, adamantyl, norbornyl, isobornyl, 2-methyl-2-adamantyl, 2-methyl-2-isobornyl, 2-butyl-2-adamantyl, 2-propyl-2-isobornyl, 2-methyl-2-tetracyclododecenyl, 2-methyl-2-dihydrodicyclopentadienyl-cyclohexyl, etc. A non-limiting example of R4 in the —OCOOR4 carbonate may be t-butoxycarbonyl. Non-limiting examples of the —OR5 ether may include tetrahydropyranyl ether, trialkylsilyl ether, etc.
In another example, the siloxane polymer of the photosensitive composition may be a copolymer having a first repeating unit represented by Formula 1 and a second repeating unit represented by Formula 2 below,
where R2 may be hydrogen, hydroxyl, a C1-C10 alkyl, a C1-C10 alkoxy, a C1-C10 haloalkyl, etc.
In another example, the siloxane polymer of the photosensitive composition may be a polymer having a chemical structure represented by Formula 3 below,
where R6 may be a divalent moiety, e.g., —(CH2)n-, —O—, —CO(CH2)n-, —COO(CH2)n-,
R7 may be t-butyl, adamantyl, norbornyl, isobornyl, 2-methyl-2-adamantyl, 2-methyl-2-isobornyl, 2-butyl-2-adamantyl, 2-propyl-2-isobornyl, 2-methyl-2-tetracyclododecenyl or 2-methyl-2-dihydrodicyclopentadienyl-cyclohexyl, R8 may be a divalent moiety, e.g., —(CH2)n-, —CO(CH2)n- and —COO(CH2)n-, R9 may be a divalent moiety, e.g., —(CH2)m-, n may be an integer from 1 to 10, and m may be an integer from 0 to 10. In Formula 3, each of p, q and r may be a positive integer, and a ratio of p, q and r may be adjusted to improve hydrophilicity of the photosensitive composition, solubility of the photosensitive composition in a developing solution, and a cross-linking of the blocking pattern. For example, the ratio of p, q and r may be about 1:1:1 to about 10:5:3.
The siloxane polymer of the photosensitive composition may have a molecular weight adjusted to improve viscosity of the photosensitive composition, coatability of the photosensitive composition on the substrate 10, etch resistance of the blocking pattern, and solubility of the photosensitive composition in a developing solution. For example, the siloxane polymer may have a weight-average molecular weight in a range of about 5,000 to about 20,000.
The cross-linking agent of the photosensitive composition may be any suitable cross-linking compound capable of initiating a cross-linking reaction in the presence of acid or heat. Non-limiting examples of the cross-linking agent may include one or more of a melamine compound, e.g., one or more of alkoxymethyl melamine, alkylated melamine, etc., a urea compound, e.g., one or more of urea, alkoxymethylene urea, N-alkoxymethylene urea, tetrahydro-1,3,4,6-tetramethylimidazo[4,5-d]imidazole-2,5-(1H,3H)-dione, ethylene urea, etc., uril, e.g., one or more of benzoguanamine, glycol uril, etc., and so forth.
The thermal acid generator of the photosensitive composition may be any suitable thermal acid generator capable of generating acid in response to an initiation of heat. A non-limiting example of the thermal acid generator may be a sulfonate compound. Non-limiting examples of the sulfonate compound may include compounds represented by Formulae 4-11. These may be used alone or in a combination thereof.
The photoacid generator of the photosensitive composition may be any suitable photoacid generator capable of generating acid when exposed to light. Non-limiting examples of the photoacid generator may include one or more of a sulfonium salt, a triarylsulfonium salt, an iodonium salt, a diaryliodonium salt, a nitrobenzyl ester, a disulfone, a diazo-disulfone, a sulfonate, trichloromethyltriazine, N-hydroxysuccinimide triflate, etc.
More specifically, non-limiting examples of the photoacid generator may include one or more of triphenylsulfonium triflate, triphenylsulfonium antimony salt, diphenyliodonium triflate, diphenyliodonium antimony salt, diphenyliodonium perfluorooctanesulfonate, methoxydiphenyliodonium triflate, pyrogallol tris(alkylsulfonate), di-t-butyldiphenyliodonium triflate, 2,6-dinitrobenzyl sulfonate, norbornene-dicarboxyimide triflate, triphenylsulfonium nonaflate, norbornene dicarboxyimide nonaflate, diphenyliodonium nonaflate, methoxydiphenyliodonium nonaflate, di-t-butyldiphenyliodonium nonaflate, N-hydroxysuccinimide nonaflate, triphenylsulfonium perfluorooctanesulfonate, methoxyphenyliodonium perfluorooctanesulfonate, di-t-butyldiphenyliodonium triflate, norbornene dicarboxyimide perfluorooctanesulfonate, N-hydroxysuccinimide perfluorooctanesulfonate, etc.
The photosensitive composition may further include an additive, e.g., a surfactant and/or an organic base, in an amount of about 0.00001 parts to about 10 parts by weight, based on about 100 parts by weight of the siloxane polymer. Non-limiting examples of the surfactant may include one or more of a polyoxyalkylene alkylether, an ammonium dodecylbenzenesulfonate, an alkylphosphate, etc. The organic base may control a diffusion distance of acid generated from the photoacid generator and/or the thermal acid generator. Non-limiting examples of the organic base may include one or more of triethylamine, triisobutylamne, triisooctylamine, triisodecylamine, diethanolamine, triethanolamine, etc.
The photosensitive composition may further include a solvent. The solvent may dissolve the above-mentioned components, and may adjust viscosity of the photosensitive composition. Non-limiting examples of the solvent may include one or more of ether, lactone, ester, ketone, alcohol, amide, sulfoxide, nitrile, aliphatic hydrocarbon and aromatic hydrocarbon.
The photosensitive composition according to example embodiments of the present invention may include a siloxane polymer, as opposed to an organic polymer with a hydrocarbon backbone, so the photosensitive composition may have increased solubility in an etching solution for removing silicon oxides, e.g., after the photosensitive composition is cured. Thus, a cured photosensitive composition according to example embodiments may be efficiently removed, i.e., substantially entirely removed from the substrate 10, using the etching solution for removing silicon oxides, so substantially no contaminants may remain on the substrate 10, as compared to a conventional composition including the organic polymer with the hydrocarbon backbone.
Once the preliminary blocking layer 12 including the photosensitive composition is formed on the substrate 10, a portion of the preliminary blocking layer 12 in the edge die region of the substrate 10 may be exposed to light, as illustrated in
The exposure process for exposing the portion of the preliminary blocking layer 12 in the edge die region of the substrate 10 to light may be performed using a reticle defining at least one reticle image that corresponds to at least one die. For convenience of description, as used herein, when a reticle image is referred to as “corresponding” to a predetermined number of dies (or chips), the reticle image may define a pattern for the predetermined number of dies. For example, a reticle image corresponding to nine dies may define a pattern for nine dies. Each of a plurality of reticle images may correspond to substantially fewer dies than a maximum number of dies that may be exposed to light in one shot (i.e., at one time). It is noted that when the substrate 10 is exposed to light using the reticle, even though a number of dies exposed to light in one shot may be relatively small and require a relatively large number of shots, since the exposure process may be performed only in the edge die region of the substrate 10, i.e., a substantially smaller area than the die forming region of the substrate 10, a total time required for performing the exposure process according to example embodiments may be relatively short.
Once the blocking pattern 14 is formed on the substrate 10 in the edge die region thereof, the substrate 10 may be developed using a developing solution to remove at least a portion of the preliminary blocking layer 12 that is disposed in the die forming region, as illustrated in
As further illustrated in
Referring to
In particular, a pattern layer (not illustrated) may be formed on the substrate 50, e.g., by a chemical vapor deposition (CVD) process, followed by formation of a photoresist film (not illustrated) on the pattern layer, e.g., by a spin-coating process. A first exposure process may be performed on the photoresist film to form a photoresist pattern (not illustrated) on the pattern layer in the die forming region and the edge die region of the substrate 50. The pattern layer may be etched using the photoresist pattern as an etching mask to form the pattern structure 52 having the openings 51 on the substrate 50. It is noted that the first exposure process may be performed using a first reticle that defines a reticle image corresponding to a maximum number of dies that may be exposed to light in one shot, i.e., first number of dies. Thus, since a relatively large number of dies may be exposed to light in one shot in the first exposure process, a total number of shots required in the first exposure process for forming the pattern structure 52 on the entire substrate 50, i.e., both the die forming region and the edge die, may be relatively small.
Referring to
Referring to
As illustrated in
Alternatively, an entire portion of the preliminary blocking layer 54 in the edge die region of the substrate 50 may be cured or cross-linked in the second exposure process to form the first preliminary blocking pattern 56 in the edge die region (not illustrated). In other words, both upper and lower portions of the first preliminary blocking pattern 56 in the edge die region of the substrate 50 may be cured by the second exposure process.
Once the blocking pattern 56 is formed on the substrate 50 in the edge die region thereof, the substrate 50 may be developed using a developing solution to remove at least a portion of the preliminary blocking layer 54 from the die forming region of the substrate 50. In particular, as illustrated in
The second preliminary blocking pattern 58 may be formed by immersing the substrate 50 in the developing solution, so the preliminary blocking layer 54 may be partially removed in the die forming region of the substrate 50. A height of the second preliminary blocking pattern 58, i.e., a distance as measured from an upper surface of the second preliminary blocking pattern 58 to an upper surface of the substrate 50, may be adjusted by changing a length of time for immersing the substrate 50 in the developing solution. For example, as illustrated in
Referring to
According to example embodiments, as illustrated in
Method of Manufacturing a Semiconductor Device
Referring to
Referring to
A transistor associated with a word line may be formed on the semiconductor substrate 100. In an exemplary formation method of the transistor, a gate oxide layer (not illustrated) may be formed on the semiconductor substrate 100 in the active region, followed by formation of a first conductive layer (not illustrated) and a first hard mask layer (not illustrated) on the gate oxide layer. The first conductive layer may function as a gate electrode, and may be formed, e.g., of one or more of polysilicon doped with impurities, tungsten, and tungsten silicide.
The first hard mask layer may be patterned through a photolithography process to form a first hard mask pattern. The first conductive layer may be etched using the first hard mask pattern as an etching mask to form the gate electrode. The gate electrode may have a line shape, and may extend along a second direction, i.e., a direction perpendicular to the first direction. As a result, a gate structure 104 including the gate oxide layer, the gate electrode, and the first hard mask pattern may be formed on the semiconductor substrate 100. It is noted that multiple gate structures 104 may be formed on the substrate 100 by a substantially same process as described above.
Once the gate structure 104 is formed, an insulation layer (not illustrated) may be formed on the semiconductor substrate 100 of, e.g., a silicon nitride. The insulation layer may be anisotropically etched to form first spacers 106 on sidewalls of the gate structure 104, as illustrated in
An ion implantation process may be performed using the gate structures 104 and the first spacers 106 as a mask to implant impurities into portions of the semiconductor substrate 100 between adjacent gate structures 104. As a result, as illustrated in
Once the transistor is formed, a first insulating interlayer 112 may be formed to cover the transistor. The first insulating interlayer 112 may be formed using silicon oxide, e.g., one or more of borophosphosilicate glass (BPSG), phosphosilicate glass (PSG), undoped silicate glass (USG), spin-on-glass (SOG), plasma-enhanced tetraethyl orthosilicate (PE-TEOS), and high-density plasma chemical vapor deposition (HDP-CVD) oxide. The first insulating interlayer 112 may be formed by, e.g., a chemical vapor deposition (CVD) process, a plasma-enhanced chemical vapor deposition (PECVD) process, a high-density plasma chemical vapor deposition (HDPCVD) process, or an atomic layer deposition (ALD) process. Once the first insulating interlayer 112 is formed, a chemical mechanical polishing (CMP) process may be performed to remove an upper portion of the first insulating interlayer 112, i.e., planarize an upper surface of the first insulating interlayer 112.
A photoresist pattern (not illustrated) may be formed on the first insulating interlayer 112, and the first insulating interlayer 112 may be etched using the photoresist pattern as an etching mask to form first contact holes (not shown) therethrough to expose source regions 108 and drain regions 110. The first contact holes may be formed through the first insulating interlayer 112 by self-alignment relative to the first spacers 106 disposed on sidewalls of the gate structures 104. The photoresist pattern may be removed from the semiconductor substrate 100 by at least one of an ashing process and a striping process.
A second conductive layer (not illustrated) may be formed on the first insulating interlayer 112 to fill the first contact holes. The second conductive layer may be formed from, e.g., polysilicon doped with impurities. An upper portion of the second conductive layer disposed on the first insulating interlayer 112 may be removed, e.g., by a CMP process, to expose an upper surface of the first insulating interlayer 112, so portions of the second conductive layer may remain in the first contact holes to define contact plugs in the first contact holes. Each one of the contact plugs may be electrically connected to one of source regions 108 or to one of drain regions 110. A contact plug making contact with one of the source regions 108 may be referred to hereinafter as a first contact plug 114, and a contact plug making contact with one of the drain regions 110 may be referred to hereinafter as a second contact plug 116. Each first contact plug 114 may be connected to a bit line, and each second contact plug 116 may be connected to a capacitor.
A second insulating interlayer 118 may be formed on the first insulating interlayer 112. The second insulating interlayer 118 may be formed using, e.g., silicon oxide. A photoresist pattern (not illustrated) may be formed on the second insulating interlayer 118. As illustrated in
Referring to
A photoresist pattern (not illustrated) may be formed on the second hard mask layer. The second hard mask layer may be etched using the photoresist pattern as an etching mask to form a second hard mask pattern 126 on the third conductive layer, followed by removal of the photoresist pattern from the second hard mask pattern 126.
The third conductive layer may be patterned using the second hard mask pattern 126 as an etching mask to form a bit line 124. The bit line 124 may include bit line contacts 122 filling the second contact holes 120, so each bit line contact 122 may connect a corresponding first contact plug 114 to the bit line 124. The bit line 124 may extend along the first direction, i.e., perpendicularly to the direction of the gate structure 104. A silicon nitride layer (not illustrated) may be formed on the bit line 124, second hard mask pattern 126, and second insulating interlayer 118, followed by anisotropic etching of the silicon nitride layer to form second spacers (not illustrated) on sidewalls of the bit line 124 and on the second hard mask pattern 126.
A third insulating interlayer 128 may be formed on the second insulating interlayer 118 and on the bit line 124. The third insulating interlayer 128 may be formed using, e.g., silicon oxide. A CMP process may be performed to planarize an upper surface of the third insulating interlayer 128. A photoresist pattern (not illustrated) may be formed on the third insulating interlayer 128, so the third insulating interlayer 128 and the second insulating interlayer 118 may be etched using the photoresist pattern as an etching mask to form third contact holes (not shown) exposing second contact plugs 116. The third contact holes may be formed through self-alignment relative to the second spacers formed on the sidewalls of the bit line 124 and the second hard mask pattern 126.
A third conductive layer (not illustrated) may be formed on the third insulating interlayer 128 to fill the third contact holes. The third conductive layer may be formed using polysilicon doped with impurities. An upper portion of the third conductive layer may be removed, e.g., by performing a CMP process, to form third contact plugs 130 in the third contact holes, so the third contact plugs 130 may connect the second contact plugs 116 to lower electrodes 140a formed in a subsequent process (see
Referring to
A mold oxide layer 134 may be formed on the etch stop layer 132. The mold oxide layer 134 may be formed by depositing an oxide, e.g., one or more of borophosphosilicate glass (BPSG), phosphosilicate glass (PSG), undoped silicate glass (USG), spin-on-glass (SOG), plasma enhanced-tetraethyl orthosilicate (PE-TEOS), etc. The mold oxide layer 134 may function as a template for forming lower electrodes 140a, and may be formed to have a substantially larger thickness, e.g., a distance as measured from an upper surface of the mold oxide layer 134 to an upper surface of the etch stop layer 132, than a height of the lower electrodes 140a to be formed subsequently.
Referring to
It is noted that the first reticle image defined by the first reticle may correspond to a maximum number of dies or chips that may be exposed through a single shot of light. Thus, a number chips that may be exposed to light through a single shot using the first reticle according to example embodiments may be relatively large. For example, as illustrated in
In contrast, in a conventional exposure process for patterning a mold oxide layer, exposure of a film only within the die forming region of the substrate, e.g., exposure in an edge die region may be minimized to reduce shifting or removal of abnormal lower electrodes in the edge die region of the substrate, may be controlled by using a reticle defining reticle images corresponding to a relatively small number of chips, e.g., one, two, or three chips. Accordingly, a relatively large number of shots may be required to sufficiently expose the film in the die forming region.
Therefore, the reticle image defined by the first reticle according to embodiments of the present invention may require only a single type of reticle image that corresponds to a larger number of chips than the conventional process, so the number of shots and the processing time required for patterning the mold oxide layer 134 may be substantially reduced. Therefore, manufacturing productivity according to example embodiments may be improved. Further, portions of the photoresist film disposed in the edge die region of the substrate 100 and exposed to light due to a relatively large number of chips defined by the reticle image, may not be shifted and/or removed due to the protection layer. Accordingly, removal or shifting of portions of lower electrodes formed in the edge die region may be prevented or substantially minimized by forming a blocking layer 144 in the edge die region of the substrate 50 in a subsequent process (See
After the first exposure process of the photoresist film is complete, a developing process and a baking process may be performed on the photoresist film to form a photoresist pattern 136 on the mold oxide layer 134. The photoresist pattern 136 may be formed in the edge die region and in the die forming region of the substrate 100.
In another example embodiment, a hard mask layer (not illustrated) may be formed on the mold oxide layer 134. The photoresist pattern 136 may be formed on the hard mask layer through processes that may be substantially the same as those described above. Then, the hard mask layer may be etched using the photoresist pattern 136 to form a hard mask pattern (not illustrated) on the mold oxide layer 134. The hard mask pattern may be formed in the edge die region as well as in the die forming region. The hard mask pattern may be used as an etching mask in a process for patterning the mold oxide layer 134.
Referring to
Referring to
In one example embodiment, the lower electrode layer 140 may be formed using a metal or a metal nitride to form a capacitor occupying a relatively small area and having a relatively high storage capacitance. In another example embodiment, the lower electrode layer 140 may be formed using polysilicon doped with impurities to improve step coverage of the lower electrode layer 140, despite a depletion layer generated between a dielectric layer and a subsequently formed lower electrode. In still another example embodiment, the lower electrode layer 140 may be a multi-layer of titanium and titanium nitride. In that embodiment, the titanium of the lower electrode layer 140, which may make direct contact with one of the third contact plugs 130, may be converted into titanium silicide through a reaction between the titanium and polysilicon of the third contact plug 130. The titanium silicide layer formed through that reaction may function as an ohmic layer.
Referring to
Use of the photosensitive composition in the preliminary blocking layer 142 may facilitate curing of the preliminary blocking layer 142 by an exposure process and/or a thermal treatment process. Further, use of the photosensitive composition may facilitate removal of the photosensitive composition, e.g., by a developing solution, prior to the exposure process or the thermal treatment process, and may facilitate removal of the cured photosensitive composition by a wet process using an etching solution that may include a fluoride compound instead of an ashing process.
Referring to
A portion of the preliminary blocking layer 142 disposed in the edge die region and exposed to light in the second exposure process may be cured through a cross-linking reaction activated by an acid generated from the photoacid generator. Thus, the exposed portion of the preliminary blocking layer 142 in the edge die region may be altered to become insoluble in the developing solution. As a result, a first preliminary blocking pattern 144 having a cured portion may be formed in the edge die region of the substrate 100. In one embodiment, only an upper portion of the preliminary blocking layer 142 disposed in the edge die region may be converted into the first preliminary blocking pattern 144, as illustrated in
It is noted that the second exposure process may be performed to expose an entire edge die region of the substrate 100 to trigger a cross-linking reaction and not for forming a fine pattern in the edge die region. Thus, the second exposure process may not require an exposure apparatus with a relatively high resolution. Rather, the second exposure process may be performed using an exposure apparatus having a relatively low resolution, i.e., having a relatively low grade. For example, the second exposure process may be performed using an I-line exposure apparatus, a KrF exposure apparatus or an ArF exposure apparatus.
Referring to
The developing process may be performed using a developing solution used in the development of photoresist. For example, the developing solution may include about 2.4 percent by weight of tetramethylammonium hydroxide and about 97.6 percent by weight of water.
Referring to
Referring to
After forming the lower electrodes 140a in the die forming region, a cleaning process may be performed to remove etching residue from the lower electrodes 140a. Referring to
In contrast, in a conventional method of forming a blocking pattern using a photoresist having an organic polymer, e.g., a methacrylate-based resin, the blocking pattern may not be readily removed by a wet etching process, thereby requiring use of an ashing process using plasma. The ashing process may cause severe damage to a lower electrode which may be exposed to plasma during the removal of the blocking pattern and may also generate polymeric contaminants that may not be easily removed from a semiconductor substrate. Example embodiments of the present invention, however, may include formation of the first and the second blocking patterns 147 and 146a of siloxane polymer, so the first and the second blocking patterns 147 and 146a may be substantially completely removed from the substrate 100 using a wet etching solution including, e.g., a fluoride compound. The wet etching solution used in removing the first and the second blocking patterns 147 and 146a may not substantially cause damage (e.g., plasma damage) to the lower electrode.
Further, the first and the second blocking patterns 147 and 146a and the mold oxide layer pattern 134a in the die forming region may be removed by the same etching process. Thus, a processing time for removing the first and the second blocking patterns 147 and 146a and the mold oxide layer pattern 134a in the die forming region may be substantially reduced, and process efficiency may be substantially improved. Further, the first and the second blocking patterns 147 and 146a having the siloxane polymer may have high solubility relative to the wet etching solution including, e.g., a fluoride compound, and thus may be readily removed during the wet etching process. Accordingly, generation of polymeric contaminants may be prevented or substantially minimized while the first and second blocking patterns 147 and 146a are removed, so defects in the semiconductor device may be substantially reduced.
By removing the mold oxide layer pattern 134a and the second blocking pattern 146a from the die forming region, a bottom, inner walls and outer walls of the lower electrode 140a may be exposed in the die forming region. In addition, a portion of the lower electrode layer 140 disposed in the edge die region may be exposed by removing the first blocking pattern 147 from the edge die region. The portion of the lower electrode layer 140 disposed in the edge die region may be continuously formed because the portion of the lower electrode layer 140 disposed under the first blocking pattern 147 may remain in the edge die region unetched. Thus, shifting or removing of the lower electrode layer 140 in the edge die region of the substrate 100 during formation of the lower electrodes 140a in the die forming region of the substrate 100 may be prevented or substantially minimized.
Referring to
An upper electrode 152 may be formed on the dielectric layer 150. The upper electrode 152 may be formed using one or more of polysilicon doped with impurities, a metal, a metal nitride, etc. The upper electrode 152 may include a material having a metal to improve a storage capacitance of a capacitor. In addition, the upper electrode 152 may, for example, be formed having a multi-layered structure including a titanium nitride film and a doped polysilicon film.
The dielectric layer 150 and the upper electrode 152 may be sequentially formed on the lower electrodes 140a to complete the formation of capacitors electrically connected to the third contact plugs 130.
A number of shots required for forming a lower electrode in accordance with an example embodiment was compared with a number of shots required for forming a lower electrode using a conventional method, i.e., using a conventional reticle defining reticle images corresponding to fewer than a maximum number of chips that may be exposed in one shot when forming a mold layer pattern.
A hard mask pattern was used to form a mold layer pattern according to an example embodiment, and a first reticle defining a reticle image was used in a first exposure process according to an example embodiment. As illustrated in
As illustrated in
In accordance with an example embodiment, only the edge die region 100b of the substrate W was additionally exposed to light in a second exposure process. A second reticle defining three types of reticle images, as illustrated in
an exposure process for forming a mold layer pattern was performed using a reticle defining varying reticle images. The reticle used in the exposure process defined three types of reticle images, i.e., reticle images 202a-202c illustrated in
It is noted that a number of shots required to perform the first exposure process on the entire substrate W according to embodiments of the present invention, i.e., substrate W in
According to example embodiments, a blocking pattern may be readily formed using a negative-type photosensitive composition having a siloxane polymer to selectively cover or block a specific region, e.g., an edge die region, of a substrate. Accordingly, shifting or removing a lower electrode which may be disposed in the edge die region may be prevented. Further, the blocking pattern and a mold layer pattern may be simultaneously removed using a wet etching solution, thereby simplifying a semiconductor manufacturing process and reducing costs thereof. Damage or deterioration of the lower electrode, which may be caused by an ashing process performed for removing a conventional blocking pattern having organic photoresist, may be prevented, and generation of polymeric contaminants may be greatly suppressed and reduced. Therefore, efficiency and productivity of the semiconductor manufacturing process may be substantially improved.
Example embodiments of the present invention have been disclosed herein, and although specific terms are employed, they are used and are to be interpreted in a generic and descriptive sense only and not for purpose of limitation. Accordingly, it will be understood by those of ordinary skill in the art that various changes in form and details may be made without departing from the spirit and scope of the present invention as set forth in the following claims.
Number | Date | Country | Kind |
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10-2007-0081623 | Aug 2007 | KR | national |